Chemistry : the molecular nature of matter and change / Martin S. Silberberg

DETAILED CONTENTS
Summary List of Special Features:
Chemical Connections; Tools of the Laboratory; Galleries; Animations; and Margin
Notes xiv
About the Author and Consultants xvii
Preface xix
Guided Tour xxii
Acknowledgments xxix
A Note to the Student: How to Do Well in This Course xxxii
Keys to the Study of Chemistry 1
1.1 Some Fundamental Definitions 3
The Properties of Matter 3
The Three States of Matter 4
The Central Theme in Chemistry 6
The Importance of Energy in the Study of Matter 6
1.2 Chemical Arts and the Origins of Modern Chemistry 8
Prechemical Traditions 8
The Phlogiston Fiasco and the Impact of Lavoisier 10
1.3 The Scientific Approach: Developing a Model 11
1.4 Chemical Problem Solving 13
Units and Conversion Factors in Calculations 13
A Systematic Approach to Solving Chemistry Problems 15
1.5 Measurement in Scientific Study 17
General Features of SI Units 17
Some Important SI Units in Chemistry 18
1.6 Uncertainty in Measurement: Significant Figures 27
Determining Which Digits Are Significant 28
Working with Significant Figures in Calculations 28
Precision, Accuracy, and Instrument Calibration 31
Chemical Connections
CHEMISTRY PROBLEM SOLVING IN THE REAL WORLD 32
Chapter Perspective 33
For Review and Reference 34
Problems 35
The Components of Matter 40
2.1 Elements, Compounds, and Mixtures: An Atomic Overview 41
2.2 The Observations That Led to an Atomic View of Matter 43
Mass Conservation 43
Definite Composition 44
Multiple Proportions 45
2.3 Dalton's Atomic Theory 46
Postulates of the Atomic Theory 46
How the Theory Explains the Mass Laws 46
The Relative Masses of Atoms 47
2.4 The Observations That Led to the Nuclear Atom Model 48
Discovery of the Electron and Its Properties 48
Discovery of the Atomic Nucleus 50
2.5 The Atomic Theory Today 51
Structure of the Atom 51
Atomic Number, Mass Number, and Atomic Symbol 52
Isotopes and Atomic Masses of the Elements 52
Tools of the Laboratory MASS SPECTROMETRY 54
A Modern Reassessment of the Atomic Theory 55
2.6 Elements: A First Look at the Periodic Table 56
2.7 Compounds: Introduction to Bonding 59
The Formation of Ionic Compounds 59
The Formation of Covalent Compounds 62
Polyatomic Ions: Covalent Bonds Within Ions 63
2.8 Compounds: Formulas, Names, and Masses 63
Types of Chemical Formulas 64
Some Advice About Learning Names and Formulas 64
Names and Formulas of Ionic Compounds 65
Names and Formulas of Binary Covalent Compounds 70
Molecular Masses from Chemical Formulas 71
Gallery PICTURING MOLECULES 73
2.9 Mixtures: Classification and Separation 74
Tools of the Laboratory BASIC SEPARATION TECHNIQUES 75
Chapter Perspective 77
For Review and Reference 78
Problems 79
Stoichiometry: Mole-Mass-Number Relationships in Chemical Systems 86
3.1 The Mole 87
Defining the Mole 87
Molar Mass 89
Interconverting Moles, Mass, and Number of Chemical Entities 90
Mass Percent from the Chemical Formula 93
3.2 Determining the Formula of an Unknown Compound 95
Empirical Formulas 95
Molecular Formulas 96
Combustion Analysis 98
Chemical Formulas and the Structures of Molecules 99
3.3 Writing and Balancing Chemical Equations 101
3.4 Calculating Amounts of Reactant and Product 105
Stoichiometrically Equivalent Molar Ratios from the Balanced Equation 106
Chemical Reactions That Occur in a Sequence 108
Chemical Reactions That Involve a Limiting Reactant 110
Chemical Reactions in Practice: Theoretical, Actual, and Percent Yields 112
3.5 Fundamentals of Solution Stoichiometry 114
Expressing Concentration in Terms of Molarity 114
Mole-Mass-Number Conversions Involving Solutions 115
Preparing and Diluting Molar Solutions 116
Stoichiometry of Chemical Reactions in Solution 118
Chapter Perspective 120
For Review and Reference 120
Problems 123
The Major Classes of Chemical Reactions 131
4.1 The Role of Water as a Solvent 132
The Solubility of Ionic Compounds 132
The Polar Nature of Water 134
4.2 Writing Equations for Aqueous Ionic Reactions 137
4.3 Precipitation Reactions 138
THE DRIVING FORCE FOR A PRECIPITATION REACTION 138
Predicting Whether a Precipitation Reaction Will Occur 139
4.4 Acid-Base Reactions 140
The Driving Force and Net Change: Formation of H2O from H1 and OH2 141
Acid-Base Titrations 143
Acid-Base Reactions as Proton-Transfer Processes 144
4.5 Oxidation-Reduction (Redox) Reactions 146
The Driving Force for Redox Processes 147
Some Essential Redox Terminology 148
Using Oxidation Numbers to Monitor the Movement of Electron Charge 148
Balancing Redox Equations 150
Redox Titrations 152
4.6 Elemental Substances in Redox Reactions 154
4.7 Reversible Reactions: An Introduction to Chemical Equilibrium 162
Chapter Perspective 164
For Review and Reference 164
Problems 166
Gases and the Kinetic-Molecular Theory 173
5.1 An Overview of the Physical States of Matter 174
5.2 Gas Pressure and Its Measurement 176
Laboratory Devices for Measuring Gas Pressure 176
Units of Pressure 178
5.3 The Gas Laws and Their Experimental Foundations 180
The Relationship Between Volume and Pressure: Boyle's Law 180
The Relationship Between Volume and Temperature: Charles's Law 181
The Relationship Between Volume and Amount: Avogadro's Law 183
Gas Behavior at Standard Conditions 184
The Ideal Gas Law 185
Solving Gas Law Problems 186
5.4 Further Applications of the Ideal Gas Law 189
The Density of a Gas 189
The Molar Mass of a Gas 191
The Partial Pressure of a Gas in a Mixture of Gases 192
5.5 The Ideal Gas Law and Reaction Stoichiometry 195
5.6 The Kinetic-Molecular Theory: A Model for Gas Behavior 197
How the Kinetic-Molecular Theory Explains the Gas Laws 197
Effusion and Diffusion 201
The Chaotic World of Gases: Mean Free Path and Collision Frequency 203
Chemical Connections Chemistry in Planetary Science: STRUCTURE AND COMPOSITION
OF THE EARTH'S ATMOSPHERE 204
5.7 Real Gases: Deviations from Ideal Behavior 207
Effects of Extreme Conditions on Gas Behavior 207
The van der Waals Equation: The Ideal Gas Law Redesigned 209
Chapter Perspective 210
For Review and Reference 210
Problems 212
Thermochemistry: Energy Flow and Chemical Change 220
6.1 Forms of Energy and Their Interconversion 221
The System and Its Surroundings 221
Energy Flow to and from a System 222
Heat and Work: Two Forms of Energy Transfer 223
The Law of Energy Conservation 225
UNITS OF ENERGY 225
State Functions and the Path Independence of the Energy Change 226
6.2 Enthalpy: Heats of Reaction and Chemical Change 228
The Meaning of Enthalpy 228
Comparing DE and DH 228
Exothermic and Endothermic Processes 229
Some Important Types of Enthalpy Change 230
Changes in Bond Strengths, or Where Does the Heat of Reaction Come From? 230
6.3 Calorimetry: Laboratory Measurement of Heats of Reaction 233
Specific Heat Capacity 233
The Practice of Calorimetry 234
6.4 Stoichiometry of Thermochemical
Equations 236
6.5 Hess's Law of Heat Summation 238
6.6 Standard Heats of Reaction (DH0rxn) 240
Formation Equations and Their Standard Enthalpy Changes 240
Determining DH0rxn from DH0f Values of Reactants and Products 241
Chemical Connections Chemistry in Environmental Science:
THE FUTURE OF ENERGY USE 243
Chapter Perspective 245
For Review and Reference 246
Problems 247
Quantum Theory and Atomic Structure 254
7.1 The Nature of Light 255
The Wave Nature of Light 256
The Particle Nature of Light 260
7.2 Atomic Spectra 262
The Bohr Model of the Hydrogen Atom 263
Limitations of the Bohr Model 264
The Energy States of the Hydrogen Atom 264
Tools of the Laboratory SPECTROPHOTOMETRY IN CHEMICAL ANALYSIS 267
7.3 The Wave-Particle Duality of Matter and Energy 269
The Wave Nature of Electrons and the Particle Nature of Photons 269
The Heisenberg Uncertainty Principle 272
7.4 The Quantum-Mechanical Model of the Atom 273
The Atomic Orbital and the Probable Location of the Electron 273
Quantum Numbers of an Atomic Orbital 275
Shapes of Atomic Orbitals 278
Energy Levels of the Hydrogen Atom 281
Chapter Perspective 281
For Review and Reference 281
Problems 283
Electron Configuration and Chemical Periodicity 288
8.1 Development of the Periodic Table 289
8.2 Characteristics of Many-Electron Atoms 290
The Electron-Spin Quantum Number 290
The Exclusion Principle 291
Electrostatic Effects and the Splitting of Energy Levels 292
8.3 The Quantum-Mechanical Model and the Periodic Table 295
BUILDING UP PERIODS 1 AND 2 295
Building Up Period 3 298
Electron Configurations Within Groups 299
The First d-Orbital Transition Series: Building Up Period 4 299
General Principles of Electron Configurations 301
Complex Patterns: The Transition and Inner Transition Elements 302
8.4 Trends in Some Key Periodic Atomic Properties 304
Trends in Atomic Size 304
Trends in Ionization Energy 307
Trends in Electron Affinity 310
8.5 The Connection Between Atomic Structure and Chemical Reactivity 311
Trends in Metallic Behavior 311
Properties of Monatomic Ions 314
Chapter Perspective 320
For Review and Reference 320
Problems 321
Models of Chemical Bonding 326
9.1 Atomic Properties and Chemical Bonds 327
Types of Chemical Bonding 327
Lewis Electron-Dot Symbols: Depicting Atoms in Chemical Bonding 329
9.2 The Ionic Bonding Model 330
Energy Considerations in Ionic Bonding: The Importance of Lattice Energy 331
Periodic Trends in Lattice Energy 333
How the Model Explains the Properties of Ionic Compounds 335
9.3 The Covalent Bonding Model 337
The Formation of a Covalent Bond 337
The Properties of a Covalent Bond: Bond Energy and Bond Length 338
How the Model Explains the Properties of Covalent Compounds 341
Tools of the Laboratory INFRARED SPECTROSCOPY 343
9.4 Between the Extremes: Electronegativity and Bond Polarity 344
Electronegativity 344
Polar Covalent Bonds and Bond Polarity 346
The Partial Ionic Character of Polar Covalent Bonds 347
The Continuum of Bonding Across a Period 348
9.5 An Introduction to Metallic Bonding 349
The Electron-Sea Model 349
How the Model Explains the Properties of Metals 350
Chapter Perspective 351
For Review and Reference 352
Problems 353
The Shapes of Molecules 357
10.1 Depicting Molecules and Ions with Lewis Structures 358
Using the Octet Rule to Write Lewis Structures 358
Resonance: Delocalized Electron-Pair Bonding 362
Formal Charge: Selecting the Best Resonance Structure 364
Lewis Structures for Exceptions to the Octet Rule 365
10.2 Using Lewis Structures and Bond Energies to Calculate
Heats of Reaction 368
10.3 Valence-Shell Electron-Pair Repulsion (VSEPR)
Theory and Molecular Shape 370
Electron-Group Arrangements and Molecular Shapes 371
THE MOLECULAR SHAPE WITH TWO ELECTRON GROUPS (LINEAR ARRANGEMENT) 372
Molecular Shapes with Three Electron Groups (Trigonal Planar Arrangement) 372
Molecular Shapes with Four Electron Groups (Tetrahedral Arrangement) 373
Molecular Shapes with Five Electron Groups (Trigonal Bipyramidal
Arrangement) 375
Molecular Shapes with Six Electron Groups (Octahedral Arrangement) 376
Using VSEPR Theory to Determine Molecular Shape 377
Molecular Shapes with More Than One Central Atom 378
Gallery Molecular Beauty: ODD SHAPES WITH USEFUL FUNCTIONS 380
10.4 Molecular Shape and Molecular Polarity 381
Bond Polarity, Bond Angle, and Dipole Moment 381
The Effect of Molecular Polarity on Behavior 383
Chapter Perspective 383
Chemical Connections
Chemistry in Sensory Physiology: MOLECULAR SHAPE, BIOLOGICAL RECEPTORS,
AND THE SENSE OF SMELL 384
For Review and Reference 386
Problems 387
Theories of Covalent Bonding 392
11.1 Valence Bond (VB) Theory and Orbital Hybridization 393
The Central Themes of VB Theory 393
Types of Hybrid Orbitals 394
11.2 The Mode of Orbital Overlap and the Types of Covalent Bonds 400
The VB Treatment of Single and Multiple Bonds 400
Orbital Overlap and Molecular Rotation 403
11.3 Molecular Orbital (MO) Theory and Electron Delocalization 404
The Central Themes of MO Theory 404
Homonuclear Diatomic Molecules of the Period 2 Elements 407
MO Description of Some Heteronuclear Diatomic Molecules 412
MO Descriptions of Ozone and Benzene 413
Chapter Perspective 414
For Review and Reference 414
Problems 416
Intermolecular Forces: Liquids, Solids, and Phase Changes 419
12.1 An Overview of Physical States and Phase Changes 420
12.2 Quantitative Aspects of Phase Changes 423
Heat Involved in Phase Changes: A Kinetic-Molecular Approach 423
The Equilibrium Nature of Phase Changes 425
Phase Diagrams: The Effect of Pressure and Temperature on Physical State 430
12.3 Types of Intermolecular Forces 431
Ion-Dipole Forces 432
Dipole-Dipole Forces 432
The Hydrogen Bond 434
Polarizability and Charge-Induced Dipole Forces 436
Dispersion (London) Forces 436
12.4 Properties of the Liquid State 439
Surface Tension 439
Capillarity 439
Viscosity 440
Gallery PROPERTIES OF LIQUIDS 441
12.5 The Uniqueness of Water 442
SOLVENT PROPERTIES OF WATER 442
Thermal Properties of Water 442
Surface Properties of Water 443
The Density of Solid and Liquid Water 443
12.6 The Solid State: Structure, Properties, and Bonding 445
Structural Features of Solids 445
Tools of the Laboratory
X-RAY DIFFRACTION ANALYSIS AND SCANNING TUNNELING MICROSCOPY 451
Types and Properties of Crystalline Solids 452
Amorphous Solids 456
Bonding in Solids: Molecular Orbital Band Theory 456
12.7 Advanced Materials 460
Electronic Materials 460
Liquid Crystals 462
Ceramic Materials 465
Polymeric Materials 468
Nanotechnology: Designing Materials Atom by Atom 473
Chapter Perspective 475
For Review and Reference 476
Problems 477
The Properties of Mixtures: Solutions and Colloids 484
13.1 Types of Solutions: Intermolecular Forces and Predicting Solubility 486
Intermolecular Forces in Solution 486
Liquid Solutions and the Role of Molecular Polarity 487
Chemical Connections
Chemistry in Pharmacology: THE MODE OF ACTION OF SOAPS AND ANTIBIOTICS 490
Gas Solutions and Solid Solutions 492
13.2 Energy Changes in the Solution Process 493
Heats of Solution and Solution Cycles 493
Heats of Hydration: Ionic Solids in Water 494
The Solution Process and the Tendency Toward Disorder 496
13.3 Solubility as an Equilibrium Process 497
Effect of Temperature on Solubility 498
Effect of Pressure on Solubility 500
13.4 Quantitative Ways of Expressing Concentration 501
Molarity and Molality 501
Parts of Solute by Parts of Solution 502
Converting Units of Concentration 504
13.5 Colligative Properties of Solutions 506
Colligative Properties of Nonvolatile Nonelectrolyte Solutions 506
Gallery COLLIGATIVE PROPERTIES IN INDUSTRY AND BIOLOGY 512
Using Colligative Properties to Find Solute Molar Mass 514
Colligative Properties of Volatile Nonelectrolyte Solutions 515
Colligative Properties of Electrolyte Solutions 516
13.6 The Structure and Properties of Colloids 517
Chapter Perspective 519
Chemical Connections
Chemistry in Sanitary Engineering: SOLUTIONS AND COLLOIDS IN WATER
PURIFICATION 520
For Review and Reference 522
Problems 524
A Perspective on the Properties of the Elements 531
Topic 1 The Key Atomic Properties 532
Topic 2 Characteristics of Chemical Bonding 534
Topic 3 Metallic Behavior 536
Topic 4 Acid-Base Behavior of the Element Oxides 537
Topic 5 Redox Behavior of the Elements 538
Topic 6 Physical States and Phase Changes 540
Periodic Patterns in the Main-Group Elements: Bonding, Structure,
and Reactivity 542
14.1 Hydrogen, the Simplest Atom 543
Where Does Hydrogen Fit in the Periodic Table? 543
Highlights of Hydrogen Chemistry 544
14.2 Trends Across the Periodic Table: The Period 2 Elements 545
14.3 Group 1A(1): The Alkali Metals 548
Why Are the Alkali Metals Soft, Low Melting, and Lightweight? 548
Why Are the Alkali Metals So Reactive? 548
The Anomalous Behavior of Lithium 549
14.4 Group 2A(2): The Alkaline Earth Metals 552
How Do the Physical Properties of the Alkaline Earth and Alkali
Metals Compare? 552
How Do the Chemical Properties of the Alkaline Earth and Alkali
Metals Compare? 552
The Anomalous Behavior of Beryllium 553
Diagonal Relationships: Lithium and Magnesium 553
Looking Backward and Forward: Groups 1A(1), 2A(2), and 3A(13) 553
14.5 Group 3A(13): The Boron Family 556
How Do the Transition Elements Influence Group 3A(13) Properties? 556
What New Features Appear in the Chemical Properties of Group 3A(13)? 556
Highlights of Boron Chemistry 560
Diagonal Relationships: Beryllium and Aluminum 562
14.6 Group 4A(14): The Carbon Family 562
How Does the Bonding in an Element Affect Physical Properties? 562
How Does the Type of Bonding Change in Group 4A(14) Compounds? 566
Highlights of Carbon Chemistry 566
Highlights of Silicon Chemistry 568
Diagonal Relationships: Boron and Silicon 569
Looking Backward and Forward: Groups 3A(13), 4A(14), and 5A(15) 569
Gallery SILICATE MINERALS AND SILICONE POLYMERS 570
14.7 Group 5A(15): The Nitrogen Family 573
What Accounts for the Wide Range of Physical Behavior in Group 5A(15)? 573
What Patterns Appear in the Chemical Behavior of Group 5A(15)? 576
Highlights of Nitrogen Chemistry 577
Highlights of Phosphorus Chemistry: Oxides and Oxoacids 580
14.8 Group 6A(16): The Oxygen Family 581
How Do the Oxygen and Nitrogen Families Compare Physically? 581
How Do the Oxygen and Nitrogen Families Compare Chemically? 584
Highlights of Oxygen Chemistry: Range of Oxide Properties 586
Highlights of Sulfur Chemistry: Oxides, Oxoacids, and Sulfides 586
Looking Backward and Forward: Groups 5A(15), 6A(16), and 7A(17) 588
14.9 Group 7A(17): The Halogens 588
What Accounts for the Regular Changes in the Halogens' Physical Properties? 588
Why Are the Halogens So Reactive? 588
Highlights of Halogen Chemistry 592
14.10 Group 8A(18): The Noble Gases 595
How Can Noble Gases Form Compounds? 595
Looking Backward and Forward: Groups 7A(17), 8A(18), and 1A(1) 595
Chapter Perspective 597
For Review and Reference 597
Problems 598
Organic Compounds and the Atomic Properties of Carbon 606
15.1 The Special Nature of Carbon and the Characteristics
of Organic Molecules 607
The Structural Complexity of Organic Molecules 608
The Chemical Diversity of Organic Molecules 608
15.2 The Structures and Classes of Hydrocarbons 610
Carbon Skeletons and Hydrogen Skins 610
Alkanes: Hydrocarbons with Only Single Bonds 613
Constitutional Isomerism and the Physical Properties of Alkanes 615
Chiral Molecules and Optical Isomerism 617
Alkenes: Hydrocarbons with Double Bonds 618
Chemical Connections
Chemistry in Sensory Physiology: GEOMETRIC ISOMERS AND THE CHEMISTRY
OF VISION 620
Alkynes: Hydrocarbons with Triple Bonds 621
Aromatic Hydrocarbons: Cyclic Molecules with Delocalized a Electrons 622
Variations on a Theme: Catenated Inorganic Hydrides 623
Tools of the Laboratory NUCLEAR MAGNETIC RESONANCE (NMR) SPECTROSCOPY 624
15.3 Some Important Classes of Organic Reactions 624
Types of Organic Reactions 624
The Redox Process in Organic Reactions 627
15.4 Properties and Reactivities of Common Functional Groups 627
Functional Groups with Single Bonds 628
Functional Groups with Double Bonds 633
Functional Groups with Both Single and
Double Bonds 635
Functional Groups with Triple Bonds 640
15.5 The Monomer-Polymer Theme I: Synthetic Macromolecules 641
Addition Polymers 642
Condensation Polymers 643
15.6 The Monomer-Polymer Theme II: Biological Macromolecules 644
Sugars and Polysaccharides 644
Amino Acids and Proteins 646
Nucleotides and Nucleic Acids 650
Chapter Perspective 654
For Review and Reference 654
Problems 656
Kinetics: Rates and Mechanisms of Chemical Reactions 663
16.1 Factors That Influence Reaction Rate 665
16.2 Expressing the Reaction Rate 667
Average, Instantaneous, and Initial Reaction Rates 668
Expressing Rate in Terms of Reactant and Product Concentrations 669
16.3 The Rate Law and Its Components 671
Tools of the Laboratory MEASURING REACTION RATES 672
Determining the Initial Rate 672
REACTION ORDER TERMINOLOGY 672
Determining Reaction Orders 675
Determining the Rate Constant 677
16.4 Integrated Rate Laws: Concentration Changes over Time 677
Integrated Rate Laws for First-, Second-, and Zero-Order Reactions 677
Determining the Reaction Order from the Integrated Rate Law 679
Reaction Half-Life 680
16.5 The Effect of Temperature on Reaction Rate 682
16.6 Explaining the Effects of Concentration and Temperature 685
Collision Theory: Basis of the Rate Law 685
Transition State Theory: Molecular Nature of the Activated State 688
16.7 Reaction Mechanisms: Steps in the Overall Reaction 691
Elementary Reactions and Molecularity 692
The Rate-Determining Step of a Reaction Mechanism 693
Correlating the Mechanism with the Rate Law 694
16.8 Catalysis: Speeding Up a Chemical Reaction 697
Homogeneous Catalysis 698
Heterogeneous Catalysis 699
Chemical Connections
Chemistry in Enzymology: KINETICS AND FUNCTION OF BIOLOGICAL CATALYSTS 700
Chemical Connections
Chemistry in Atmospheric Science: DEPLETION OF THE EARTH'S OZONE LAYER 702
Chapter Perspective 703
For Review and Reference 703
Problems 705
Equilibrium: The Extent of Chemical Reactions 713
17.1 The Dynamic Nature of the Equilibrium State 714
17.2 The Reaction Quotient and the Equilibrium Constant 717
Writing the Reaction Quotient 718
Variations in the Form of the Reaction Quotient 719
17.3 Expressing Equilibria with Pressure Terms: Relation Between Kc and Kp 724
17.4 Reaction Direction: Comparing Q and K 725
17.5 How to Solve Equilibrium Problems 727
Using Quantities to Determine the Equilibrium Constant 727
Using the Equilibrium Constant to Determine Quantities 730
17.6 Reaction Conditions and the Equilibrium State:
Le ChYtelier's Principle 736
The Effect of a Change in Concentration 737
The Effect of a Change in Pressure (Volume) 739
The Effect of a Change in Temperature 741
The Lack of Effect of a Catalyst 743
Chemical Connections
Chemistry in Industrial Production: THE HABER PROCESS FOR
THE SYNTHESIS OF AMMONIA 744
Chemical Connections
Chemistry in Cellular Metabolism: DESIGN AND CONTROL OF A METABOLIC PATHWAY 745
Chapter Perspective 747
For Review and Reference 747
Problems 749
Acid-Base Equilibria 756
18.1 Acids and Bases in Water 758
Proton or Hydroxide Ion Release and the Classical Acid-Base Definition 759
Variation in Acid Strength: The Acid-Dissociation Constant (Ka) 759
Classifying the Relative Strengths of Acids and Bases 762
18.2 Autoionization of Water and the pH Scale 764
THE EQUILIBRIUM NATURE OF AUTOIONIZATION: THE
ION-PRODUCT CONSTANT FOR WATER (KW) 764
Expressing the Hydronium Ion Concentration: The pH Scale 765
18.3 Proton Transfer and the Bronsted-Lowry Acid-Base Definition 768
The Conjugate Acid-Base Pair 769
Relative Acid-Base Strength and the Net Direction of Reaction 770
18.4 Solving Problems Involving Weak-Acid Equilibria 772
Finding Ka Given Concentrations 773
Finding Concentrations Given Ka 775
The Effect of Concentration on the Extent of Acid Dissociation 776
The Behavior of Polyprotic Acids 776
18.5 Weak Bases and Their Relation to Weak Acids 779
Molecules as Weak Bases: Ammonia and the Amines 779
Anions of Weak Acids as Weak Bases 782
The Relation Between Ka and Kb of a Conjugate Acid-Base Pair 782
18.6 Molecular Properties and Acid Strength 784
Trends in Acid Strength of Nonmetal Hydrides 784
Trends in Acid Strength of Oxoacids 785
Acidity of Hydrated Metal Ions 786
18.7 Acid-Base Properties of Salt Solutions 787
Salts That Yield Neutral Solutions 787
Salts That Yield Acidic Solutions 787
Salts That Yield Basic Solutions 788
Salts of Weakly Acidic Cations and Weakly Basic Anions 789
18.8 Generalizing the Bronsted-Lowry Concept: The Leveling Effect 790
18.9 Electron-Pair Donation and the Lewis Acid-Base Definition 791
Molecules as Lewis Acids 792
Metal Cations as Lewis Acids 793
An Overview of Acid-Base Definitions 794
Chapter Perspective 795
For Review and Reference 795
Problems 797
Ionic Equilibria in Aqueous Systems 805
19.1 Equilibria of Acid-Base Buffer Systems 806
How a Buffer Works: The Common-Ion Effect 806
The Henderson-Hasselbalch Equation 811
Buffer Capacity and Buffer Range 812
Preparing a Buffer 813
19.2 Acid-Base Titration Curves 815
Monitoring pH with Acid-Base Indicators 815
Strong Acid-Strong Base Titration Curves 816
Weak Acid-Strong Base Titration Curves 818
Weak Base-Strong Acid Titration Curves 821
Titration Curves for Polyprotic Acids 822
Amino Acids as Biological Polyprotic Acids 823
19.3 Equilibria of Slightly Soluble Ionic Compounds 824
The Ion-Product Expression (Qsp) and the Solubility-Product Constant (Ksp) 824
Calculations Involving the Solubility-Product Constant 826
The Effect of a Common Ion on Solubility 828
The Effect of pH on Solubility 829
Predicting the Formation of a Precipitate: Qsp vs. Ksp 830
Chemical Connections
Chemistry in Geology: CREATION OF A LIMESTONE CAVE 831
Chemical Connections
Chemistry in Environmental Science: THE ACID-RAIN PROBLEM 833
19.4 Equilibria Involving Complex Ions 835
Formation of Complex Ions 835
Complex Ions and the Solubility of Precipitates 837
Complex Ions of Amphoteric Hydroxides 838
19.5 Application of Ionic Equilibria to Chemical Analysis 840
Selective Precipitation 840
Qualitative Analysis: Identifying Ions in Complex Mixtures 841
Chapter Perspective 846
For Review and Reference 846
Problems 848
Thermodynamics: Entropy, Free Energy, and the Direction of Chemical
Reactions 855
20.1 The Second Law of Thermodynamics: Predicting Spontaneous Change 856
Limitations of the First Law of Thermodynamics 857
The Sign of DH Cannot Predict Spontaneous Change 858
Disorder and Entropy 859
Entropy and the Second Law of Thermodynamics 861
Standard Molar Entropies and the Third Law 861
20.2 Calculating the Change in Entropy of a Reaction 866
Entropy Changes in the System: The Standard Entropy of Reaction (DSorxn) 866
Entropy Changes in the Surroundings: The Other Part of the Total 867
Chemical Connections Chemistry in Biology: DO LIVING THINGS OBEY THE LAWS
OF THERMODYNAMICS? 869
The Entropy Change and the Equilibrium State 870
Spontaneous Exothermic and Endothermic Reactions: A Summary 870
20.3 Entropy, Free Energy, and Work 872
Free Energy Change and Reaction Spontaneity 872
Calculating Standard Free Energy Changes 873
DG and the Work a System Can Do 874
The Effect of Temperature on Reaction Spontaneity 876
Coupling of Reactions to Drive a Nonspontaneous Change 878
Chemical Connections
Chemistry in Biological Energetics: THE UNIVERSAL ROLE OF ATP 879
20.4 Free Energy, Equilibrium, and Reaction Direction 880
Chapter Perspective 884
For Review and Reference 884
Problems 886
Electrochemistry: Chemical Change and Electrical Work 892
21.1 Half-Reactions and Electrochemical Cells 893
A Quick Review of Oxidation-Reduction Concepts 893
Half-Reaction Method for Balancing Redox
Reactions 894
An Overview of Electrochemical Cells 898
21.2 Voltaic Cells: Using Spontaneous Reactions to Generate Electrical
Energy 900
Construction and Operation of a Voltaic Cell 900
Notation for a Voltaic Cell 903
Why Does a Voltaic Cell Work? 904
21.3 Cell Potential: Output of a Voltaic Cell 905
Standard Cell Potentials 906
Relative Strengths of Oxidizing and Reducing Agents 908
21.4 Free Energy and Electrical Work 914
STANDARD CELL POTENTIAL AND THE EQUILIBRIUM CONSTANT 914
The Effect of Concentration on Cell Potential 916
Cell Potential and the Relation Between Q and K 918
Concentration Cells 919
21.5 Electrochemical Processes in Batteries 922
Gallery BATTERIES AND THEIR APPLICATIONS 923
21.6 Corrosion: A Case of Environmental Electrochemistry 926
The Corrosion of Iron 926
Protecting Against the Corrosion of Iron 927
21.7 Electrolytic Cells: Using Electrical Energy to Drive a Nonspontaneous
Reaction 929
Construction and Operation of an Electrolytic Cell 929
Predicting the Products of Electrolysis 931
The Stoichiometry of Electrolysis: The Relation Between Amounts of Charge
and Product 935
Chemical Connections
Chemistry in Biological Energetics: CELLULAR ELECTROCHEMISTRY AND THE
PRODUCTION OF ATP 937
Chapter Perspective 939
For Review and Reference 939
Problems 942
The Elements in Nature and Industry 950
22.1 How the Elements Occur in Nature 951
Earth's Structure and the Abundance of the Elements 951
Sources of the Elements 955
22.2 The Cycling of Elements Through the Environment 956
The Carbon Cycle 956
The Nitrogen Cycle 958
The Phosphorus Cycle 960
22.3 Metallurgy: Extracting a Metal from Its Ore 963
Pretreating the Ore 963
Converting Mineral to Element 964
Refining and Alloying the Element 967
22.4 Tapping the Crust: Isolation and Uses of the Elements 968
Producing the Alkali Metals: Sodium and Potassium 968
The Indispensable Three: Iron, Copper, and Aluminum 970
Mining the Sea: Magnesium and Bromine 977
The Many Sources and Uses of Hydrogen 978
A Group at a Glance: Sources, Isolation, and Uses of the Elements 981
22.5 Chemical Manufacturing: Two Case Studies 987
Sulfuric Acid, the Most Important Chemical 987
The Chlor-Alkali Process 990
Chapter Perspective 991
For Review and Reference 992
Problems 993
The Transition Elements and Their Coordination Compounds 998
23.1 Properties of the Transition Elements 1000
Electron Configurations of the Transition Metals and Their Ions 1000
Atomic and Physical Properties of the Transition Elements 1002
Chemical Properties of the Transition Metals 1003
23.2 The Inner Transition Elements 1006
THE LANTHANIDES 1006
The Actinides 1007
23.3 Highlights of Selected Transition Metals 1008
Chromium 1008
Manganese 1009
Silver 1010
Mercury 1012
23.4 Coordination Compounds 1013
Structures of Complex Ions: Coordination Numbers, Geometries, and Ligands 1014
Formulas and Names of Coordination Compounds 1016
A Historical Perspective: Alfred Werner and Coordination Theory 1018
Isomerism in Coordination Compounds 1020
23.5 Theoretical Basis for the Bonding and Properties of Complexes 1023
Application of Valence Bond Theory to Complex Ions 1023
Crystal Field Theory 1025
Chapter Perspective 1031
Chemical Connections
Chemistry in Nutritional Science: TRANSITION METALS AS ESSENTIAL DIETARY TRACE
ELEMENTS 1032
For Review and Reference 1034
Problems 1035
Nuclear Reactions and Their Applications 1040
24.1 Radioactive Decay and Nuclear Stability 1042
The Components of the Nucleus: Terms and Notation 1042
The Discovery of Radioactivity and the Types of Emissions 1042
Types of Radioactive Decay; Balancing Nuclear Equations 1044
Nuclear Stability and the Mode of Decay 1046
24.2 The Kinetics of Radioactive Decay 1050
The Rate of Radioactive Decay 1050
Tools of the Laboratory COUNTERS FOR THE DETECTION OF RADIOACTIVE EMISSIONS 1051
Radioisotopic Dating 1053
24.3 Nuclear Transmutation: Induced Changes in Nuclei 1055
Early Transmutation Experiments; Discovery of the Neutron 1055
Particle Accelerators and the Transuranium Elements 1056
24.4 The Effects of Nuclear Radiation on Matter 1058
The Effects of Radioactive Emissions: Excitation and Ionization 1058
Effects of Ionizing Radiation on Living Matter 1058
24.5 Applications of Radioisotopes 1062
Radioactive Tracers: Applications of Nonionizing Radiation 1062
Applications of Ionizing Radiation 1065
24.6 The Interconversion of Mass and Energy 1066
The Mass Defect 1066
Nuclear Binding Energy 1067
24.7 Applications of Fission and Fusion 1069
The Process of Nuclear Fission 1069
THE PROMISE OF NUCLEAR FUSION 1073
Chemical Connections
Chemistry in Cosmology: ORIGIN OF THE ELEMENTS IN THE STARS 1074
Chapter Perspective 1076
For Review and Reference 1077
Problems 1079
Appendix A Common Mathematical Operations in Chemistry A-1
Manipulating Logarithms A-1
Using Exponential (Scientific) Notation A-2
Solving Quadratic Equations A-3
Graphing Data in the Form of a Straight Line A-4
Appendix B Standard Thermodynamic Values for Selected Substances at 298 K A-5
Appendix C Solubility-Product Constants (Ksp) of Slightly Soluble Ionic
Compounds at 298 K A-8
Appendix D Standard Electrode (Half-Cell) Potentials at 298 K A-9
Appendix E Answers to Selected Problems A-10
Glossary G-1
Credits C-1
Index I-1
SUMMARY LIST OF SPECIAL FEATURES
Chemical Connections
Chemistry Problem Solving in the Real World 32
Chemistry in Planetary Science: Structure and Composition of the Earth's
Atmosphere 204
Chemistry in Environmental Science: The Future of Energy Use 243
Chemistry in Sensory Physiology: Molecular Shape, Biological Receptors, and the
Sense of Smell 384
Chemistry in Pharmacology: The Mode of Action of Soaps and Antibiotics 490
Chemistry in Sanitary Engineering: Solutions and Colloids in Water
Purification 520
Chemistry in Sensory Physiology: Geometric Isomers and the Chemistry of
Vision 620
Chemistry in Enzymology: Kinetics and Function of Biological Catalysts 700
Chemistry in Atmospheric Science: Depletion of the Earth's Ozone Layer 702
Chemistry in Industrial Production: The Haber Process for the Synthesis of
Ammonia 744
Chemistry in Cellular Metabolism: Design and Control of a Metabolic Pathway 745
Chemistry in Geology: Creation of a Limestone Cave 831
Chemistry in Environmental Science: The Acid-Rain Problem 833
Chemistry in Biology: Do Living Things Obey the Laws of Thermodynamics? 869
Chemistry in Biological Energetics: The Universal Role of ATP 879
Chemistry in Biological Energetics: Cellular Electrochemistry and the Production
of ATP 937
Chemistry in Nutritional Science: Transition Metals as Essential Dietary Trace
Elements 1032
Chemistry in Cosmology: Origins of the Elements in the Stars 1074
Tools of the Laboratory Mass Spectrometry 54
Basic Separation Techniques 75
Spectrophotometry in Chemical Analysis 267
Infrared Spectroscopy 343
X-Ray Diffraction Analysis and Scanning Tunneling Microscopy 451
Nuclear Magnetic Resonance (NMR) Spectroscopy 624
Measuring Reaction Rates 672
Counters for the Detection of Radioactive Emissions 1051
Galleries Picturing Molecules 73
Molecular Beauty: Odd Shapes with Useful Functions 380
Properties of Liquids 441
Colligative Properties in Industry and Biology 512
Silicate Minerals and Silicone Polymers 570
Batteries and Their Applications 923
Animations and Other Media
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Chapter 1
The three states of matter 4
Chapter 2
Rutherford's experiment 51
Formation of an ionic compound 60
Chapter 3
Limiting reactant 111
Making a solution 116
Chapter 4
Dissolution of an ionic compound and a covalent compound 135
Precipitation reactions 139
Chapter 5
Properties of gases 184
Chapter 6
Energy flow 229
Chapter 7
Emission spectra 264
Atomic line specta 281
Chapter 8
Isoelectronic series 319
Chapter 9
Formation of an ionic compound 328
Formation of a covalent bond 341
Ionic vs. covalent bonding 346
Chapter 10
VSEPR theory and the shapes of molecules 376
VSEPR 376
Influence of shape on polarity 382
Polarity of molecules 382
Chapter 11
Molecular shapes and orbital hybridization 398
Chapter 12
Vapor pressure 426
Phase diagrams and the states of matter 431
Cubic unit cells and their origins 454
Chapter 17
Le ChYtelier's principle 741
Chapter 18
Dissociation of strong and weak acids 761
Chapter 19
Acid-base titration 818
Chapter 21
Galvanic cell 903
Operation of a voltaic cell 903
Chapter 22
Thermite reaction 966
Iron smelting 971
Aluminum production 975
Chapter 23
Vanadium reduction 1004
Chapter 24
Radioactive decay 1043
Half-life 1053
Nuclear power 1073
Margin Notes
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note appearing in the margin.
Chapter 1
The Incredible Range of Physical Change 5
Scientific Thinker Extraordinaire [Lavoisier] 10
A Great Chemist Yet Strict Phlogistonist [Priestley] 11
Everyday Scientific Thinking 13
How Many Barleycorns from His Majesty's Nose to His Thumb? [Inexact units] 17
How Long Is a Meter? 19
Don't Drop That Kilogram! 21
Central Importance of Measurement in Science [Lord Kelvin] 27
Chapter 2
Immeasurable Changes in Mass 44
Dalton's Revival of Atomism 46
Atoms? Humbug! [Famous skeptics] 47
Familiar Glow of Colliding Particles [Signs, aurora, and TV] 48
The "Big Three" Subatomic Particles 51
Naming an Element 52
The Heresy of Radioactive "Transmutation" 56
Chapter 3
Imagine a Mole of . . . [Amazing comparisons] 87
A Rose by Any Other Name [Natural product formulas] 95
Limiting Reactants in Everyday Life 111
Chapter 4
Solid Solvents for Ions 135
Displacement Reactions Inside You [Protein metabolism] 142
Space-Age Combustion Without a Flame [Fuel cells] 160
Chapter 5
Atmosphere-Biosphere Redox Interconnections 174
POW! P-s-s-s-t! POP! [Familiar effects of gas behavior] 175
Snowshoes and the Meaning of Pressure 176
The Mystery of the Suction Pump 177
Breathing and the Gas Laws 184
Gas Density and Human Disasters 189
Up, Up, and Away! [Hot-air balloons] 190
Preparing Nuclear Fuel 202
Danger on Molecular Highways [Molecular motion] 203
Chapter 6
Wherever You Look There Is a System 221
Thermodynamics in the Kitchen 223
The Tragic Life of the First Law's Discoverer [von Mayer] 225
Your Personal Financial State Function [Checkbook analogy] 227
Imagine an Earth Without Water [Specific heat capacity] 236
Chapter 7
Hooray for the Human Mind [Major events around 1900] 255
Electromagnetic Emissions Everywhere 257
Rainbows and Diamonds 259
Ping-Pong Photons [Analogy for photoelectric effect] 261
What Are Stars Made Of? 266
"He'll Never Make a Success of Anything" [Einstein] 269
The Electron Microscope 270
Uncertainty Is Unacceptable? [Famous skeptics] 273
A Radial Probability Distribution of Apples 275
Chapter 8
Mendeleev's Great Contribution 289
Moseley and Atomic Number 290
Baseball Quantum Numbers [Analogy with stadium seat] 291
Periodic Memory Aids 302
Packing 'Em In [Nuclear charge and atomic size] 306
Chapter 9
The Remarkable Insights of G. N. Lewis 330
The Amazing Malleability of Gold 351
Chapter 10
A Purple Mule, Not a Blue Horse and a Red Donkey [Resonance hybrid] 362
Deadly Free-Radical Activity 365
Chapter 12
Environmental Flow [Solid, liquid, and gas flow] 421
Frozen Gold 421
Cooling Phase Change [Sweating and panting] 422
Cooking Under Low or High Pressure 429
The Remarkable Behavior of a Supercritical Fluid (SCF) 431
A Diamond Film on Every Pot 456
Solar Cells 460
One Strand or Many Pieces? 468
Chapter 13
Waxes for Home and Auto 493
Hot Packs, Cold Packs, and Self-Heating Soup 496
A Saturated Solution Is Like a Pure Liquid and Its Vapor 498
Scuba Diving and Soda Pop 500
Unhealthy Ultralow Concentrations [Pollutants] 503
"Soaps" in Your Small Intestine [Bile salts] 518
From Colloid to Civilization [River deltas] 519
Chapter 14
Fill 'Er Up with Hydrogen? Not Likely 545
Versatile Magnesium 552
Lime: The Most Useful Metal Oxide 552
Gallium Arsenide: The Next Wave of Semiconductors 556
Borates in Your Labware 560
CFCs: The Good, the Bad, and the Strong 567
Hydrazine, Nitrogen's Other Hydride 576
Nitric Oxide: A Biochemical Surprise 578
The Countless Uses of Phosphates 580
Match Heads, Bug Sprays, and O-Rings 581
Selenium and Xerography 584
Hydrogen Peroxide: Hydrazine's Cousin 585
Acid from the Sky 586
HF: Unusual Structure, Familiar Uses 592
Pyrotechnic Perchlorates 594
Chapter 15
"Organic Chemistry Is Enough to Drive One Mad" [Wohler] 607
Chiral Medicines 618
Aromatic Carcinogens 623
Pollutants in the Food Chain [PCBs and DDT] 630
A Pungent, Pleasant Banquet [Carboxylic acids and esters] 638
Polysaccharide Skeletons of Lobsters and Roaches 645
Chapter 16
The Significance of R [Dimensional analysis] 683
Sleeping Through the Rate-Determining Step 693
Catalytically Cleaning Your Car's Exhaust 699
Chapter 17
The Universality of Le ChYtelier's Principle 737
Temperature-Dependent Systems [Similar math expressions] 743
Catalyzed Perpetual Motion? 743
Chapter 18
Pioneers of Acid-Base Chemistry 757
Logarithmic Scales in Sound and Seismology 765
Ammonia's Picturesque Past 779
Chapter 20
Vital Orderly Information [DNA and gene repair] 859
Poker and Probability 860
A Checkbook Analogy for Heating the Surroundings 867
Greatness and Obscurity of J. Willard Gibbs 872
The Wide Range of Energy Efficiency 875
Chapter 21
The Electrochemical Future Is Here 893
Which Half-Reaction Occurs at Which Electrode? 898
Electron Flow and Water Flow 904
The Pain of a Dental Voltaic Cell 913
Walther Hermann Nernst (1864-1941) 917
Concentration Cells in Your Nerve Cells 920
Minimicroanalysis 922
Father of Electrochemistry and Much More [Michael Faraday] 935
Chapter 22
Phosphorus from Outer Space [Meteorite sources] 960
Phosphorus Nerve Poisons 962
Panning and Fleecing for Gold 964
A Plentiful Oceanic Supply of NaCl 969
Was It Slag That Made the Great Ship Go Down? [Titanic] 971
The Dawns of Three New Ages [Copper, bronze, and brass] 972
Energy Received and Returned [Aluminum batteries] 975
Chapter 23
A Remarkable Laboratory Feat [Isolating lanthanides] 1006
Sharing the Ocean's Wealth [Manganese nodules] 1010
Mad as a Hatter [Mercury poisoning] 1013
Grabbing Ions [Chelates] 1016
Anticancer Geometric Isomers 1021
Chapter 24
The Remarkably Tiny, Massive Nucleus 1042
Her Brilliant Career [Marie Curie] 1043
The Little Neutral One [Neutrinos] 1045
The Case of the Shroud of Turin 1054
How Old Is the Solar System? 1055
The Powerful Bevatron 1057
Naming Transuranium Elements 1058
A Tragic Way to Tell Time in the Dark [Painting watch dials] 1059
The Risk of Radon 1061
Modeling Radiation Risk 1062
The Force That Binds Us [Strong force] 1067
Lise Meitner (1878-1968) 1069
"Breeding" Nuclear Fuel 1073