Chemistry: Structure and Properties; Mastering Chemistry

1158 Pages·2017·70.315 MB·English

by  Nivaldo J. Tro

8A18 2He 4.003 10Ne 20.18 18Ar 39.9536Kr 83.8054Xe 131.29 86Rn [222.02] 118Og[294] 71Lu 174.97 103Lr [262.11]
7A17 9F 19.00 17Cl 35.4535Br 79.9053I 126.90 85At [209.99] 117Ts[294] 70Yb 173.05 102No [259.10]
roups 6A16 8O 16.00 16S 32.0634Se 78.9752Te 127.60 84Po [208.98] 116Lv [292] 69Tm 168.93 101Md [258.10]
g
Main 5A15 7N 14.01 15P 30.9733As 74.9251Sb 121.76 83Bi 208.98 115Mc[289] 68Er 167.26 100Fm [257.10] ded
n
e
4A14 6C 12.01 14Si 28.0932Ge 72.6350Sn 118.71 82Pb 207.2 114Fl [289] 67Ho 164.93 99Es [252.08] recomm ments.
3A13 5B 10.81 13Al 26.9831Ga 69.7249In 114.82 81Tl 204.38 113Nh[284] 66Dy 162.50 98Cf [251.08] re those ctive ele
a a
metals 1B2B1211 2930CuZn 63.5565.384847CdAg 112.41107.87 8079HgAu 200.59196.97 111112RgCn [285][272] 6564TbGd 158.93157.25 9796BkCm [247.07][247.07] w these (1, 2, etc.) nt isotope of radio
MetalloidsNon Transition metals 8B7B1087925262728MnFeCoNi 54.94 55.8558.9358.6946434445PdTcRuRh 106.42[98]101.07102.9175767778ReOsIrPt 186.21192.22190.23195.08 107108109110BhHsMtDs [268.14][264.12][271][269.13] 63606162EuNdPmSm151.96144.24[145]150.36 95929394Am UNpPu[243.06]238.03[237.05][244.06] on American usage. The labels belod Applied Chemistry. of the longest-lived or most importa
Metals 4B5B6B456222324TiVCr 47.8750.9452.00 404142ZrNbMo 91.2292.9195.95737472TaWHf 178.49180.95183.84 104105106RfDbSg [261.11][262.11][266.12] 5859eriesCePr 140.12140.91 9091esThPa 232.04231.04 p (1A, 2A, etc.) are commnational Union of Pure ann brackets are the masses
roups 2A2 4Be 9.012 12Mg3B324.312120ScCa 44.9640.083938YSr 87.6288.915756LaBa 138.91137.33 8988RaAc [226.03][227.03] Lanthanide s Actinide seri aThe labels on to by the InterAtomic masses i
g
Main a1A1 1H 1.008 3Li 6.94 11Na 22.99 19K 39.10 37Rb 85.47 55Cs 132.91 87Fr 223.02]
[
1 2 3 4 5 6 7
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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
Astatine At 85 209.99a Neptunium Np 93 237.05a
Barium Ba 56 137.33 Nickel Ni 28 58.69
Berkelium Bk 97 247.07a Nihonium 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 Oganesson 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 Radon 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 Tennessine 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.
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CHEMISTRY
STRUCTURE AND PROPERTIES
Second Edition
Nivaldo J. Tro
WESTMONT COLLEGE
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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
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About the Author
N
ivaldo 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 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
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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
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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 ∆E in a Bomb Calorimeter
rxn
E.7 Unit Conversion 9.7 Stoichiometry Involving ∆H
E.8 Unit Conversions Involving Units Raised to a Power 9.8 Measuring ∆H in a Coffee-Cup Calorimeter
rxn
E.9 Density as a Conversion Factor 9.10 Calculating ∆H from Bond Energies
rxn
E.11 Problems with Equations 9.12 ∆H ° and Standard Enthalpies of Formation
rxn
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
1.7 The Mole Concept—Converting between Mass and Number of
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
11.1 Dipole–Dipole Forces
2.3 Wavelength, Energy, and Frequency
11.2 Hydrogen Bonding
2.5 Quantum Numbers I
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 Periodic Table 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
12.4 Relating Density to Crystal Structure
3.9 First Ionization Energy
13.3 Using Parts by Mass in Calculations
4.3 Writing Formulas for Ionic Compounds
13.4 Calculating Concentrations
4.10 The Mole Concept—Converting between Mass and Number of
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
Concentration of a Reactant at a Given Time
5.5 Writing Resonance Structures
14.8 Using the Two-Point Form of the Arrhenius Equation
5.6 Assigning Formal Charges
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 Molecule Is Polar 15.8 Finding Equilibrium Concentrations When You Know the
Equilibrium Constant and All but One of the Equilibrium
6.3 Hybridization and Bonding Scheme
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 [H O+] or [OH-]
3
9.2 Temperature Changes and Heat Capacity 16.5 Finding the [H O+] of a Weak Acid Solution
3
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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
16.12 Finding the [OH-] and pH of a Weak Base Solution Using ∆G r°xn = ∆H r°xn - T∆S r°xn
16.14 Finding the pH of a Solution Containing an Anion Acting as 18.10 Calculating ∆Grxn 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 K
sp
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 [H O] and pH of Strong and Weak Acid Solutions
3
5.8 VSEPR Theory: The Effect of Lone Pairs 16.9 The Acid–Base Properties of Ions and Salts
6.2 Valence 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
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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
E
and Analysis 33 Answers to Conceptual Connections 33
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
1.2 Classifying Matter: A Particulate View 37
The Standard Units 4 The Meter: A Measure of Length 4
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
Cathode Rays 45 Millikan’s Oil Drop Experiment: The Charge
E.6 Energy and Its Units 15
of the Electron 46
The Nature of Energy 15 Energy Units 16
1.7 The Structure of the Atom 48
Quantifying Changes in Energy 17
1.8 Subatomic Particles: Protons, Neutrons, and Electrons 50
E.7 Converting between Units 18
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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