Main groups Main groups

a 1A 8A 1 18 1 2 H 1 2A Metals Metalloids Nonmetals 3A 4A 5A 6A 7A He 1.008 2 13 14 15 16 17 4.003 3 4 5 6 7 8 9 10 2 Li Be B C N O F Ne 6.94 9.012 Transition metals 10.81 12.01 14.01 16.00 19.00 20.18 11 12 13 14 15 16 17 18 3 Na Mg 3B 4B 5B 6B 7B 8B 1B 2B Al Si P S Cl Ar 22.99 24.31 3 4567 8 9 10 11 12 26.98 28.09 30.97 32.06 35.45 39.95 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr 39.10 40.08 44.96 47.87 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.38 69.72 72.63 74.92 78.97 79.90 83.80 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe 85.47 87.62 88.91 91.22 92.91 95.95 [98] 101.07 102.91 106.42 107.87 112.41 114.82 118.71 121.76 127.60 126.90 131.29 55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 6 Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn 132.91 137.33 138.91 178.49 180.95 183.84 186.21 190.23 192.22 195.08 196.97 200.59 204.38 207.2 208.98 [208.98] [209.99] [222.02] 87 88 89 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 7 Fr RaAc Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og [223.02] [226.03] [227.03] [261.11] [262.11] [266.12] [264.12] [269.13] [268.14] [271] [272] [285] [284] [289] [289] [292] [294] [294]

58 59 60 61 62 63 64 65 66 67 68 69 70 71 Lanthanide series Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu 140.12 140.91 144.24 [145] 150.36 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.05 174.97 90 91 92 93 94 95 96 97 98 99 100 101 102 103 Actinide series Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr 232.04 231.04 238.03 [237.05] [244.06] [243.06] [247.07] [247.07] [251.08] [252.08] [257.10] [258.10] [259.10] [262.11]

a The labels on top (1A, 2A, etc.) are common American usage. The labels below these (1, 2, etc.) are those recommended by the International Union of Pure and Applied . Atomic masses in brackets are the masses of the longest-lived or most important isotope of radioactive elements. List of Elements with Their Symbols and Atomic Masses

Atomic Atomic Atomic Atomic Element Symbol Number Mass Element Symbol Number Mass Actinium Ac 89 227.03a Mendelevium Md 101 258.10a Aluminum Al 13 26.98 Mercury Hg 80 200.59 Americium Am 95 243.06a Molybdenum Mo 42 95.95 Antimony Sb 51 121.76 Moscovium Mc 115 289a Argon Ar 18 39.95 Neodymium Nd 60 144.24 Arsenic As 33 74.92 Neon Ne 10 20.18 At 85 209.99a Neptunium Np 93 237.05a Barium Ba 56 137.33 Nickel Ni 28 58.69 Berkelium Bk 97 247.07a Nh 113 284a Beryllium Be 4 9.012 Niobium Nb 41 92.91 Bismuth Bi 83 208.98 Nitrogen N 7 14.01 Bohrium Bh 107 264.12a Nobelium No 102 259.10a Boron B 5 10.81 Og 118 294a Bromine Br 35 79.90 Osmium Os 76 190.23 Cadmium Cd 48 112.41 Oxygen O 8 16.00 Calcium Ca 20 40.08 Palladium Pd 46 106.42 Californium Cf 98 251.08a Phosphorus P 15 30.97 Carbon C 6 12.01 Platinum Pt 78 195.08 Cerium Ce 58 140.12 Plutonium Pu 94 244.06a Cesium Cs 55 132.91 Polonium Po 84 208.98a Chlorine Cl 17 35.45 Potassium K 19 39.10 Chromium Cr 24 52.00 Praseodymium Pr 59 140.91 Cobalt Co 27 58.93 Promethium Pm 61 145a Copernicium Cn 112 285a Protactinium Pa 91 231.04 Copper Cu 29 63.55 Radium Ra 88 226.03a Curium Cm 96 247.07a Rn 86 222.02a Darmstadtium Ds 110 271a Rhenium Re 75 186.21 Dubnium Db 105 262.11a Rhodium Rh 45 102.91 Dysprosium Dy 66 162.50 Roentgenium Rg 111 272a Einsteinium Es 99 252.08a Rubidium Rb 37 85.47 Erbium Er 68 167.26 Ruthenium Ru 44 101.07 Europium Eu 63 151.96 Rutherfordium Rf 104 261.11a Fermium Fm 100 257.10a Samarium Sm 62 150.36 Flerovium Fl 114 289a Scandium Sc 21 44.96 Fluorine F 9 19.00 Seaborgium Sg 106 266.12a Francium Fr 87 223.02a Selenium Se 34 78.97 Gadolinium Gd 64 157.25 Silicon Si 14 28.09 Gallium Ga 31 69.72 Silver Ag 47 107.87 Germanium Ge 32 72.63 Sodium Na 11 22.99 Gold Au 79 196.97 Strontium Sr 38 87.62 Hafnium Hf 72 178.49 Sulfur S 16 32.06 Hassium Hs 108 269.13a Tantalum Ta 73 180.95 Helium He 2 4.003 Technetium Tc 43 98a Holmium Ho 67 164.93 Tellurium Te 52 127.60 Hydrogen H 1 1.008 Ts 117 294a Indium In 49 114.82 Terbium Tb 65 158.93 Iodine I 53 126.90 Thallium Tl 81 204.38 Iridium Ir 77 192.22 Thorium Th 90 232.04 Iron Fe 26 55.85 Thulium Tm 69 168.93 Krypton Kr 36 83.80 Tin Sn 50 118.71 Lanthanum La 57 138.91 Titanium Ti 22 47.87 Lawrencium Lr 103 262.11a Tungsten W 74 183.84 Lead Pb 82 207.2 Uranium U 92 238.03 Lithium Li 3 6.94 Vanadium V 23 50.94 Livermorium Lv 116 292a Xenon Xe 54 131.293 Lutetium Lu 71 174.97 Ytterbium Yb 70 173.05 Magnesium Mg 12 24.31 Yttrium Y 39 88.91 Manganese Mn 25 54.94 Zinc Zn 30 65.38 Meitnerium Mt 109 268.14a Zirconium Zr 40 91.22 aMass of longest-lived or most important isotope. CHEMISTRY STRUCTURE AND PROPERTIES

Second Edition

Nivaldo J. Tro WESTMONT COLLEGE Courseware Portfolio Management Director: Jeanne Zalesky Senior Mastering Media Producer: Jayne Sportelli Executive Courseware Portfolio Manager: Terry Haugen Rights and Permissions Manager: Ben Ferrini Courseware Director, Content Development: Jennifer Hart Rights and Permissions Management: Cenveo Publisher Services Development Editor: Erin Mulligan Photo Researcher: Eric Schrader Courseware Analyst: Coleen Morrison Production Management and Composition: codeMantra Portfolio Management Assistant: Lindsey Pruett Design Managers: Marilyn Perry, Maria Guglielmo Walsh Portfolio Management Assistant: Shercian Kinosian Cover and Interior Designer: Jeff Puda VP, Product Strategy & Development: Lauren Fogel Contributing Illustrators: Lachina Content Producers: Lisa Pierce, Mae Lum Manufacturing Buyer: Maura Zaldivar-Garcia Managing Producer: Kristen Flathman Product Marketer: Elizabeth Bell Director, Production & Digital Studio: Laura Tommasi Executive Field Marketing Manager: Chris Barker Editorial Content Producer: Jackie Jakob Cover Art: Quade Paul Director, Production & Digital Studio: Katie Foley

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Library of Congress Cataloging-in-Publication Data

Names: Tro, Nivaldo J. Title: Chemistry : structure and properties / Nivaldo J. Tro. Description: Second edition. | Hoboken, NJ : Pearson, [2018] | Includes index. Identifiers: LCCN 2016043206 | ISBN 9780134293936 Subjects: LCSH: Chemistry—Textbooks. Classification: LCC QD33.2.T7595 2018 | DDC 540—dc23 LC record available at https://lccn.loc.gov/2016043206

Student Edition: ISBN 10: 0-134-29393-2; ISBN 13: 978-0-134-29393-6 Books A La Carte Edition: ISBN 10: 0-134-52822-0; ISBN 13: 978-0-134-52822-9 1 16 www.pearsonhighered.com About the Author

ivaldo Tro is a professor of chemistry at Westmont

College in Santa Barbara, California, where he has been Na 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

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 P etroleum Research Fund, from the 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. In his lei-

sure time, Professor Tro enjoys mountain biking, surfing, and being outdoors with his family.

To Ann, Michael, Ali, Kyle, and Kaden

iii Brief Contents

E Essentials: Units, Measurement, and Problem Solving 3 1 Atoms 35 2 The Quantum-Mechanical Model of the Atom 75 3 Periodic Properties of the Elements 113 4 Molecules and Compounds 159 5 Chemical Bonding I 205 6 Chemical Bonding II 251 7 Chemical Reactions and Chemical Quantities 287 8 Introduction to Solutions and Aqueous Reactions 319 9 Thermochemistry 367 10 Gases 415 11 Liquids, Solids, and Intermolecular Forces 463 12 Crystalline Solids and Modern Materials 505 13 Solutions 539 14 Chemical Kinetics 585 15 Chemical Equilibrium 639 16 Acids and Bases 685 17 Aqueous Ionic Equilibrium 739 18 Free Energy and Thermodynamics 797 19 Electrochemistry 845 20 Radioactivity and Nuclear Chemistry 893 21 Organic Chemistry 935 22 Transition Metals and Coordination Compounds 985

Appendix I Common Mathematical Operations in Chemistry A-1 Appendix II Useful Data A-7 Appendix III Answers to Selected End-of-Chapter Problems A-19 Appendix VI Answers to In-Chapter Practice Problems A-53

Glossary G-1 Credits C-1 Index I-1

iv Interactive Media Contents

Interactive Worked Examples (IWEs)

E.3 Determining the Number of Significant Figures in a Number 9.3 Thermal Energy Transfer

E.4 Significant Figures in Calculations 9.5 Measuring ∆Erxn in a Bomb Calorimeter E.7 Unit Conversion 9.7 Stoichiometry Involving ∆H

E.8 Unit Conversions Involving Units Raised to a Power 9.8 Measuring ∆Hrxn in a Coffee-Cup Calorimeter E.9 Density as a Conversion Factor 9.10 Calculating ∆Hrxn from Bond Energies E.11 Problems with Equations 9.12 ∆H rxn° and Standard Enthalpies of Formation 1.3 Atomic Numbers, Mass Numbers, and Isotope Symbols 10.5 Ideal Gas Law I 1.4 Atomic Mass 10.7 Density of a Gas The Mole Concept—Converting between Mass and Number of 1.7 10.8 Molar Mass of a Gas Atoms 10.13 Graham’s Law of Effusion 1.8 The Mole Concept 10.14 Gases in Chemical Reactions 2.2 Photon Energy 2.3 Wavelength, Energy, and Frequency 11.1 Dipole–Dipole Forces 2.5 Quantum Numbers I 11.2 Hydrogen Bonding 2.7 Wavelength of Light for a Transition in the Hydrogen Atom 11.3 Using the Heat of Vaporization in Calculations 3.4 Writing Electron Configurations from the 11.5 Using the Two-Point Form of the Clausius–Clapeyron Equation to Predict the Vapor Pressure at a Given Temperature 3.6 Atomic Size 11.6 Navigation within a Phase Diagram 3.7 Electron Configurations and Magnetic Properties for Ions Relating Density to Crystal Structure 3.9 First Ionization Energy 12.4 4.3 Writing Formulas for Ionic Compounds 13.3 Using Parts by Mass in Calculations 4.10 The Mole Concept—Converting between Mass and Number of 13.4 Calculating Concentrations Molecules 13.5 Converting between Concentration Units 4.13 Chemical Formulas as Conversion Factors 13.6 Calculating the Vapor Pressure of a Solution Containing a 4.15 Obtaining an Empirical Formula from Experimental Data Nonvolatile Nonelectrolyte Solute 4.18 Obtaining an Empirical Formula from Combustion Analysis 13.9 Boiling Point Elevation 5.2 Writing Lewis Structures 14.2 Determining the Order and Rate Constant of a Reaction 5.4 Writing Lewis Structures for Polyatomic Ions 14.4 The First-Order Integrated Rate Law: Determining the 5.5 Writing Structures Concentration of a Reactant at a Given Time 5.6 Assigning Formal Charges 14.8 Using the Two-Point Form of the Arrhenius Equation 5.8 Writing Lewis Structures for Compounds Having Expanded 14.9 Reaction Mechanisms Octets 15.1 Expressing Equilibrium Constants for Chemical Equations 5.10 Predicting Molecular Geometries 15.5 Finding Equilibrium Constants from Experimental Concentration 5.12 Predicting the Shape of Larger Molecules Measurements 5.13 Determining If a Is Polar 15.8 Finding Equilibrium Concentrations When You Know the 6.3 Hybridization and Bonding Scheme Equilibrium Constant and All but One of the Equilibrium Concentrations of the Reactants and Products 6.5 Molecular Orbital Theory 15.9 Finding Equilibrium Concentrations from Initial Concentrations 7.2 Balancing Chemical Equations and the Equilibrium Constant 7.4 Stoichiometry 15.12 Finding Equilibrium Concentrations from Initial Concentrations 7.6 Limiting Reactant and Theoretical Yield in Cases with a Small Equilibrium Constant 8.1 Calculating Solution Concentration 15.14 The Effect of a Concentration Change on Equilibrium 8.2 Using Molarity in Calculations 16.1 Identifying Brønsted–Lowry Acids and Bases and Their 8.4 Solution Stoichiometry Conjugates + - 8.6 Writing Equations for Precipitation Reactions 16.3 Calculating pH from [H3O ] or [OH ] + 9.2 Temperature Changes and Heat Capacity 16.5 Finding the [H3O ] of a Weak Acid Solution www.pearson.com v vi Interactive Media Contents

16.7 Finding the pH of a Weak Acid Solution in Cases Where the 18.4 Calculating Gibbs Free Energy Changes and Predicting x is small Approximation Does Not Work Spontaneity from ∆H and ∆S

16.8 Finding the Equilibrium Constant from pH 18.5 Calculating Standard Entropy Changes (∆S rxn° ) 16.9 Finding the Percent Ionization of a Weak Acid 18.6 Calculating the Standard Change in Free Energy for a Reaction - ∆G° = ∆H° - T∆S° 16.12 Finding the [OH ] and pH of a Weak Base Solution Using rxn rxn rxn ∆G 16.14 Finding the pH of a Solution Containing an Anion Acting as 18.10 Calculating rxn under Nonstandard Conditions a Base 18.11 The Equilibrium Constant and ∆G rxn° 17.2 Calculating the pH of a Buffer Solution as an Equilibrium 19.2 Half-Reaction Method of Balancing Aqueous Redox Equations Problem and with the Henderson–Hasselbalch Equation in Acidic Solution 17.3 Calculating the pH Change in a Buffer Solution after the 19.3 Balancing Redox Reactions Occurring in Basic Solution Addition of a Small Amount of Strong Acid or Base 19.4 Calculating Standard Potentials for Electrochemical Cells 17.4 Using the Henderson–Hasselbalch Equation to Calculate the from Standard Electrode Potentials of the Half-Reactions pH of a Buffer Solution Composed of a Weak Base and Its 19.6 Relating ∆G ° and E ° Conjugate Acid cell 20.4 Radioactive Decay Kinetics 17.6 Strong Base–Strong Acid Titration pH Curve 20.5 Using Radiocarbon Dating to Estimate Age 17.7 Weak Acid–Strong Base Titration pH Curve 21.3 Naming Alkanes 17.8 Calculating Molar Solubility from Ksp

Key Concept Videos (KCVs)

E.8 Solving Chemical Problems 10.4 Simple Gas Laws and Ideal Gas Law 1.1 Structure Determines Properties 10.5 Simple Gas Laws and Ideal Gas Law 1.2 Classifying Matter 10.7 Mixtures of Gases and Partial Pressures 1.5 Atomic Theory 11.3 Intermolecular Forces 1.8 Subatomic Particles and Isotope Symbols 11.5 Vaporization and Vapor Pressure 1.10 The Mole Concept 11.7 Heating Curve for Water 2.2 The Nature of Light 11.8 Phase Diagrams 2.4 The Wave Nature of Matter 12.3 Unit Cells: Simple Cubic, Body-Centered Cubic, and Face-Centered Cubic 2.5 Quantum Mechanics and the Atom: Orbitals and Quantum Numbers 13.4 Solution Equilibrium and the Factors Affecting Solubility 3.3 Electron Configurations 13.5 Solution Concentration: Molarity, Molality, Parts by Mass and Volume, Mole Fraction 3.4 Writing an Electron Configuration Based on an Element’s Position on the Periodic Table 13.6 Colligative Properties 3.6 Periodic Trends in the Size of Atoms and Effective 14.4 The Rate Law for a Chemical Reaction Nuclear Charge 14.5 The Integrated Rate Law 4.4 The Lewis Model for Chemical Bonding 14.6 The Effect of Temperature on Reaction Rate 4.6 Naming Ionic Compounds 15.3 The Equilibrium Constant 4.8 Naming Molecular Compounds 15.8 Finding Equilibrium Concentrations from Initial Concentrations 5.3 Writing Lewis Structures for Molecular Compounds 15.9 Le Châtelier’s Principle 5.4 Resonance and Formal Charge 16.3 Definitions of Acids and Bases

5.7 VSEPR Theory 16.7 Finding the [H3O] and pH of Strong and Weak Acid Solutions 5.8 VSEPR Theory: The Effect of Lone Pairs 16.9 The Acid–Base Properties of Ions and Salts 6.2 Bond Theory 17.2 Buffers 6.3 Valence Bond Theory: Hybridization 17.2 Finding pH and pH Changes in Buffer Solutions 7.3 Writing and Balancing Chemical Equations 17.4 The Titration of a Weak Acid and a Strong Base 7.4 Reaction Stoichiometry 18.3 Entropy and the Second Law of Thermodynamics 7.5 Limiting Reactant, Theoretical Yield, and Percent Yield 18.4 Standard Molar Entropies 8.5 Reactions in Solution 18.6 The Effect of ∆H, ∆S, and T on Reaction Spontaneity 9.3 The First Law of Thermodynamics 18.3 Entropy and the Second Law of Thermodynamics 9.4 Heat Capacity 19.4 Standard Electrode Potentials 9.6 The Change in Enthalpy for a Chemical Reaction 19.5 Cell Potential, Free Energy, and the Equilibrium Constant 10.2 Kinetic Molecular Theory 20.3 Types of Radioactivity Contents

Preface xviii EXERCISES Review Questions 28 Problems by Topic 28 Cumulative Problems 31 Challenge Problems 32 Conceptual Problems 32 Questions for Group Work 33 Data Interpretation and Analysis 33 Answers to Conceptual Connections 33 E Essentials: Units, Measurement, and Problem Solving 3 1 Atoms 35

E.1 The Metric Mix-up: A $125 Million Unit Error 3 1.1 A Particulate View of the World: Structure Determines Properties 35 E.2 The Units of Measurement 4 The Standard Units 4 The Meter: A Measure of Length 4 1.2 Classifying Matter: A Particulate View 37 The Kilogram: A Measure of Mass 5 The Second: A Measure The States of Matter: Solid, Liquid, and Gas 37 of Time 5 The Kelvin: A Measure of Temperature 5 Elements, Compounds, and Mixtures 38 Prefix Multipliers 6 Units of Volume 7 1.3 The Scientific Approach to Knowledge 39 E.3 The Reliability of a Measurement 8 Creativity and Subjectivity in Science 40 Reporting Measurements to Reflect Certainty 8 1.4 Early Ideas about the Building Blocks of Matter 41 Precision and Accuracy 9 1.5 Modern Atomic Theory and the Laws That Led to It 41 E.4 Significant Figures in Calculations 10 The Law of Conservation of Mass 42 The Law of Definite Counting Significant Figures 10 Exact Numbers 11 Proportions 43 The Law of Multiple Proportions 44 Significant Figures in Calculations 12 John Dalton and the Atomic Theory 45 E.5 Density 14 1.6 The Discovery of the Electron 45 E.6 Energy and Its Units 15 Cathode Rays 45 Millikan’s Oil Drop Experiment: The Charge of the Electron 46 The Nature of Energy 15 Energy Units 16 Quantifying Changes in Energy 17 1.7 The Structure of the Atom 48 E.7 Converting between Units 18 1.8 Subatomic Particles: Protons, Neutrons, and Electrons 50 Elements: Defined by Their Numbers of Protons 50 Isotopes: E.8 Problem-Solving Strategies 20 When the Number of Neutrons Varies 52 Ions: Losing and Units Raised to a Power 22 Order-of-Magnitude Estimations 23 Gaining Electrons 54 E.9 Solving Problems Involving Equations 24 1.9 Atomic Mass: The Average Mass of an Element’s Atoms 54 REVIEW Self-Assessment 26 Key Learning Outcomes 27 Mass Spectrometry: Measuring the Mass of Atoms and Key Terms 27 Key Concepts 27 Key Equations and Relationships 28 Molecules 55

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