Principles of Chemistry: A Molecular Approach

937 Pages·080.001 MB·English

by  Nivaldo J. Tro

Main groups Main groups
1Aa 8A
1 18
1 2
1 H 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 4 5 6 7 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 Ra Ac Rf Db Sg Bh Hs Mt Ds Rg Cn Fl Lv
[223.02] [226.03] [227.03] [261.11] [262.11] [266.12] [264.12] [269.13] [268.14] [271] [272] [285] [289] [292]
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]
aThe 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 Chemistry.
Atomic masses in brackets are the masses of the longest-lived or most important isotope of radioactive elements.
*Element 117 is currently under review by IUPAC.
List of Elements with Their Symbols and Atomic Masses
Atomic Atomic
Element Symbol Number Atomic Mass Element Symbol Number Atomic Mass
Actinium Ac 89 227.03a Meitnerium Mt 109 268.14a
Aluminum Al 13 26.98 Mendelevium Md 101 258.10a
Americium Am 95 243.06a Mercury Hg 80 200.59
Antimony Sb 51 121.76 Molybdenum Mo 42 95.95
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 Niobium Nb 41 92.91
Beryllium Be 4 9.012 Nitrogen N 7 14.01
Bismuth Bi 83 208.98 Nobelium No 102 259.10a
Bohrium Bh 107 264.12a Osmium Os 76 190.23
Boron B 5 10.81 Oxygen O 8 16.00
Bromine Br 35 79.90 Palladium Pd 46 106.42
Cadmium Cd 48 112.41 Phosphorus P 15 30.97
Calcium Ca 20 40.08 Platinum Pt 78 195.08
Californium Cf 98 251.08a Plutonium Pu 94 244.06a
Carbon C 6 12.01 Polonium Po 84 208.98a
Cerium Ce 58 140.12 Potassium K 19 39.10
Cesium Cs 55 132.91 Praseodymium Pr 59 140.91
Chlorine Cl 17 35.45 Promethium Pm 61 145a
Chromium Cr 24 52.00 Protactinium Pa 91 231.04
Cobalt Co 27 58.93 Radium Ra 88 226.03a
Copernicium Cn 112 285a Radon Rn 86 222.02a
Copper Cu 29 63.55 Rhenium Re 75 186.21
Curium Cm 96 247.07a Rhodium Rh 45 102.91
Darmstadtium Ds 110 271a Roentgenium Rg 111 272a
Dubnium Db 105 262.11a Rubidium Rb 37 85.47
Dysprosium Dy 66 162.50 Ruthenium Ru 44 101.07
Einsteinium Es 99 252.08a Rutherfordium Rf 104 261.11a
Erbium Er 68 167.26 Samarium Sm 62 150.36
Europium Eu 63 151.96 Scandium Sc 21 44.96
Fermium Fm 100 257.10a Seaborgium Sg 106 266.12a
Flerovium Fl 114 289a Selenium Se 34 78.97
Fluorine F 9 19.00 Silicon Si 14 28.09
Francium Fr 87 223.02a Silver Ag 47 107.87
Gadolinium Gd 64 157.25 Sodium Na 11 22.99
Gallium Ga 31 69.72 Strontium Sr 38 87.62
Germanium Ge 32 72.63 Sulfur S 16 32.06
Gold Au 79 196.97 Tantalum Ta 73 180.95
Hafnium Hf 72 178.49 Technetium Tc 43 98a
Hassium Hs 108 269.13a Tellurium Te 52 127.60
Helium He 2 4.003 Terbium Tb 65 158.93
Holmium Ho 67 164.93 Thallium Tl 81 204.38
Hydrogen H 1 1.008 Thorium Th 90 232.04
Indium In 49 114.82 Thulium Tm 69 168.93
Iodine I 53 126.90 Tin Sn 50 118.71
Iridium Ir 77 192.22 Titanium Ti 22 47.87
Iron Fe 26 55.85 Tungsten W 74 183.84
Krypton Kr 36 83.80 Uranium U 92 238.03
Lanthanum La 57 138.91 Vanadium V 23 50.94
Lawrencium Lr 103 262.11a Xenon Xe 54 131.293
Lead Pb 82 207.2 Ytterbium Yb 70 173.05
Lithium Li 3 6.94 Yttrium Y 39 88.91
Livermorium Lv 116 292a Zinc Zn 30 65.38
Lutetium Lu 71 174.97 Zirconium Zr 40 91.22
Magnesium Mg 12 24.31 *b 113 284a
Manganese Mn 25 54.94 *b 115 288a
a Mass of longest-lived or most important isotope.
b The names of these elements have not yet been decided.
Principles of Chemistry
A Molecular Approach
Third ediTion
NivAldo J. Tro
Westmont College
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Library of Congress Cataloging-in-Publication Data
Tro, Nivaldo J.
Principles of Chemistry : a molecular approach / Nivaldo J. Tro, WestmontCollege. -- Third edition.
p cm
ISBN 978-0-321-97194-4
1. Chemistry, Physical and theoretical--Textbooks. 2. Chemistry, Physical and theoretical--Study and
teaching (Higher) I. Title.
QD453.3.T76 2016
540--dc23
2014040200
1 2 3 4 5 6 7 8 9 10—V011—16 15 14 13 12
ISBN 10: 0-321-97194-9; ISBN 13: 978-0-32197194-4
www.pearsonhighered.com
To Michael, Ali, Kyle, and Kaden
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 mole-
cules 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 solu-
tion. 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 out-
standing 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 leisure time, Professor Tro enjoys mountain biking, surfing,
reading to his children, and being outdoors with his family.
iii
Brief Contents
Preface xv
1 Matter, Measurement, and Problem Solving 2
2 Atoms and Elements 42
3 Molecules, Compounds, and Chemical Equations 76
4 Chemical Quantities and Aqueous Reactions 124
5 Gases 176
6 Thermochemistry 220
7 The Quantum-Mechanical Model of the Atom 262
8 Periodic Properties of the Elements 300
9 Chemical Bonding I: The Lewis Model 340
10 Chemical Bonding II: Molecular Shapes, Valence Bond Theory, and
Molecular Orbital Theory
378
11 Liquids, Solids, and Intermolecular Forces 428
12 Solutions 478
13 Chemical Kinetics 518
14 Chemical Equilibrium 562
15 Acids and Bases 602
16 Aqueous Ionic Equilibrium 646
17 Free Energy and Thermodynamics 692
18 Electrochemistry 734
19 Radioactivity and Nuclear Chemistry 776
Appendix I: Common Mathematical Operations in Chemistry A-1
Appendix II: Useful Data A-7
Appendix III: Answers to Selected Exercises A-17
Appendix IV: Answers to In-Chapter Practice Problems A-42
Glossary G-1
Credits C-1
Index i-1
iv
Contents
Preface xv
1 Matter, Measurement,
and Problem Solving
2
1.1 Atoms and Molecules 3
1.2 The Scientific Approach to Knowledge 5
1.3 The Classification of Matter 7
The States of Matter: Solid, Liquid, and Gas 7 Classifying
Matter According to Its Composition: Elements, Compounds,
and Mixtures 8
1.4 Physical and Chemical Changes and
Physical and Chemical Properties 9
1.5 Energy: A Fundamental Part of Physical and 2 Atoms and Elements
42
Chemical Change 12
1.6 The Units of Measurement 13 2.1 imaging and Moving individual Atoms 43
The Standard Units 13 The Meter: A Measure of Length 14 2.2 Modern Atomic Theory and the laws
The Kilogram: A Measure of Mass 14 The Second: A That led to it 45
Measure of Time 14 The Kelvin: A Measure of The Law of Conservation of Mass 45 The Law of Definite
Temperature 14 Prefix Multipliers 16 Derived Units: Volume Proportions 46 The Law of Multiple Proportions 47 John
and Density 17 Volume 17 Density 18 Calculating Dalton and the Atomic Theory 48
Density 18
2.3 The discovery of the Electron 48
1.7 The reliability of a Measurement 19
Cathode Rays 49 Millikan’s Oil Drop Experiment:
Counting Significant Figures 21 Exact Numbers 22 The Charge of the Electron 50
Significant Figures in Calculations 23 Precision and
2.4 The Structure of the Atom 50
Accuracy 24
2.5 Subatomic Particles: Protons, Neutrons, and
1.8 Solving Chemical Problems 25
Electrons in Atoms 52
Converting from One Unit to Another 25 General Problem-
Elements: Defined by Their Numbers of Protons 53
Solving Strategy 27 Units Raised to a Power 29
Isotopes: When the Number of Neutrons Varies 54
Problems Involving an Equation 30
Ions: Losing and Gaining Electrons 56
Chapter in review 33
2.6 Finding Patterns: The Periodic law and
Key Terms 33 Key Concepts 33 Key Equations and the Periodic Table 57
Relationships 34 Key Learning Objectives 34
Ions and the Periodic Table 59
Exercises 34
2.7 Atomic Mass: The Average Mass of an
Problems by Topic 34 Cumulative Problems 38 Element’s Atoms 61
Challenge Problems 39 Conceptual Problems 40
2.8 Molar Mass: Counting Atoms by Weighing Them 62
Questions for Group Work 41 Answers to Conceptual
Connections 41 The Mole: A Chemist’s “Dozen” 62 Converting between
Number of Moles and Number of Atoms 63 Converting
between Mass and Amount (Number of Moles) 64
Chapter in review 68
Key Terms 68 Key Concepts 69 Key Equations and
Relationships 69 Key Learning Objectives 69
Exercises 70
Problems by Topic 70 Cumulative Problems 72
Challenge Problems 73 Conceptual Problems 74
Questions for Group Work 74 Answers to Conceptual
Connections 75
v
vi Contents
3 Molecules, Compounds, and
Chemical Equations
76
3.1 Hydrogen, oxygen, and Water 77
3.2 Chemical Bonds 79
Ionic Bonds 79 Covalent Bonds 80
3.3 representing Compounds: Chemical Formulas
and Molecular Models 80
Types of Chemical Formulas 80 Molecular Models 82
3.4 An Atomic-level view of Elements and Compounds 82
3.5 ionic Compounds: Formulas and Names 86
Writing Formulas for Ionic Compounds 87 Naming Ionic
Compounds 87 Naming Binary Ionic Compounds 4 Chemical Quantities and
Containing a Metal That Forms Only One Type of Cation 89
Naming Binary Ionic Compounds Containing a Metal That Aqueous reactions
124
Forms More Than One Kind of Cation 90 Naming Ionic
Compounds Containing Polyatomic Ions 91 Hydrated Ionic 4.1 Climate Change and the Combustion of Fossil Fuels 125
Compounds 92
4.2 reaction Stoichiometry: How Much
3.6 Molecular Compounds: Formulas and Names 93 Carbon dioxide? 127
Naming Molecular Compounds 93 Naming Acids 94 Making Pizza: The Relationships Among Ingredients 127
Naming Binary Acids 95 Naming Oxyacids 95 Making Molecules: Mole-to-Mole Conversions 128
3.7 Formula Mass and the Mole Concept Making Molecules: Mass-to-Mass Conversions 128
for Compounds 96 4.3 limiting reactant, Theoretical Yield, and
Molar Mass of a Compound 97 Using Molar Mass Percent Yield 131
to Count Molecules by Weighing 97 Limiting Reactant, Theoretical Yield, and Percent Yield
3.8 Composition of Compounds 99 from Initial Reactant Masses 133
Conversion Factors from Chemical Formulas 101 4.4 Solution Concentration and Solution Stoichiometry 137
3.9 determining a Chemical Formula from Solution Concentration 138 Using Molarity in
Experimental data 102 Calculations 139 Solution Stoichiometry 143
Calculating Molecular Formulas for 4.5 Types of Aqueous Solutions and Solubility 144
Compounds 104 Combustion Analysis 105 Electrolyte and Nonelectrolyte Solutions 145 The Solubility
3.10 Writing and Balancing Chemical Equations 107 of Ionic Compounds 146
Writing Balanced Chemical Equations 109 4.6 Precipitation reactions 148
3.11 organic Compounds 111 4.7 representing Aqueous reactions: Molecular, ionic,
and Complete ionic Equations 152
Chapter in review 114
Key Terms 114 Key Concepts 114 Key Equations 4.8 Acid–Base and Gas-Evolution reactions 154
and Relationships 115 Key Learning Objectives 116 Acid–Base Reactions 154 Gas-Evolution Reactions 157
Exercises 117 4.9 oxidation–reduction reactions 159
Problems by Topic 117 Cumulative Problems 120 Oxidation States 161 Identifying Redox Reactions 163
Challenge Problems 121 Conceptual Problems 122 Combustion Reactions 165
Questions for Group Work 122 Answers to Conceptual
Chapter in review 167
Connections 122
Key Terms 167 Key Concepts 167 Key Equations and
Relationships 168 Key Learning Objectives 168
Exercises 168
Problems by Topic 168 Cumulative Problems 172
Challenge Problems 173 Conceptual Problems 174
Questions for Group Work 175 Answers to Conceptual
Connections 175
5 Gases
176
5.1 Breathing: Putting Pressure to Work 177
5.2 Pressure: The result of Molecular Collisions 178
Pressure Units 179
Contents vii
6.4 Quantifying Heat and Work 230
Heat 230 Thermal Energy Transfer 232 Work:
Pressure–Volume Work 234
6.5 Measuring 𝚫E for Chemical reactions: Constant-
volume Calorimetry 235
6.6 Enthalpy: The Heat Evolved in a Chemical reaction at
Constant Pressure 238
Exothermic and Endothermic Processes: A Molecular
View 240 Stoichiometry Involving ∆H: Thermochemical
Equations 241
6.7 Constant-Pressure Calorimetry: Measuring 𝚫Hrxn 242
6.8 Hess’s law and other relationships
involving 𝚫Hrxn 244
5.3 The Simple Gas laws: Boyle’s law, Charles’s law, 6.9 Enthalpies of reaction from Standard
and Avogadro’s law 180 Heats of Formation 247
Boyle’s Law: Volume and Pressure 181 Charles’s Law: Standard States and Standard Enthalpy Changes 247
Volume and Temperature 183 Avogadro’s Law: Volume and Calculating the Standard Enthalpy Change for a Reaction 249
Amount (in Moles) 185
Chapter in review 253
5.4 The ideal Gas law 186
Key Terms 253 Key Concepts 253 Key Equations and
5.5 Applications of the ideal Gas law: Molar volume, Relationships 254 Key Learning Objectives 254
density, and Molar Mass of a Gas 188
Exercises 255
Molar Volume at Standard Temperature and Pressure 189
Problems by Topic 255 Cumulative Problems 258
Density of a Gas 189 Molar Mass of a Gas 191
Challenge Problems 259 Conceptual Problems 260
5.6 Mixtures of Gases and Partial Pressures 192 Questions for Group Work 260 Answers to Conceptual
Collecting Gases over Water 196 Connections 261
5.7 Gases in Chemical reactions: Stoichiometry
revisited 198
Molar Volume and Stoichiometry 200
5.8 Kinetic Molecular Theory: A Model for Gases 201
The Nature of Pressure 202 Boyle’s Law 202 Charles’s
Law 202 Avogadro’s Law 202 Dalton’s Law 202
Temperature and Molecular Velocities 203
5.9 Mean Free Path, diffusion, and
Effusion of Gases 205
5.10 real Gases: The Effects of Size and intermolecular
Forces 207
The Effect of the Finite Volume of Gas Particles 207 The Effect
of Intermolecular Forces 208 Van der Waals Equation 209
Chapter in review 210
Key Terms 210 Key Concepts 210 Key Equations and
Relationships 211 Key Learning Objectives 211 7 The Quantum-Mechanical Model
Exercises 212
of the Atom
Problems by Topic 212 Cumulative Problems 215 262
Challenge Problems 217 Conceptual Problems 218
Questions for Group Work 218 Answers to Conceptual 7.1 Schrödinger’s Cat 264
Connections 219 7.2 The Nature of light 264
The Wave Nature of Light 265 The Electromagnetic
6 Thermochemistry
220 Spectrum 267 Interference and Diffraction 268 The
Particle Nature of Light 270
6.1 Chemical Hand Warmers 221
7.3 Atomic Spectroscopy and the Bohr Model 273
6.2 The Nature of Energy: Key definitions 222
7.4 The Wave Nature of Matter: The de Broglie Wavelength,
Units of Energy 224 the Uncertainty Principle, and indeterminacy 275
6.3 The First law of Thermodynamics: There is The de Broglie Wavelength 276 The Uncertainty
No Free lunch 225 Principle 277 Indeterminacy and Probability Distribution
Internal Energy 225 Maps 279