Chemistry : principles and reactions

Front Cover......Page 1
Periodic Table of the Elements......Page 2
Copyright Page......Page 6
Title Page......Page 7
Dedication Page......Page 8
Brief Contents......Page 9
CONTENTS......Page 11
Preface......Page 19
To the Student......Page 25
1 Matter and Measurements......Page 31
Elements......Page 32
Compounds......Page 34
Mixtures......Page 35
Instruments and Units......Page 37
Uncertainties in Measurements: Significant Figures......Page 39
Conversion of Units......Page 42
1.3 Properties of Substances......Page 45
Density......Page 46
Solubility......Page 48
Beyond the Classroom: Arsenic......Page 51
Key Equations......Page 52
Questions and Problems......Page 53
2 Atoms, Molecules, and Ions......Page 57
Electrons......Page 58
Protons and Neutrons; the Atomic Nucleus......Page 60
The Human Side: John Dalton......Page 59
Mass Numbers; Isotopes......Page 61
Isotopic Abundances......Page 63
Masses of Individual Atoms; Avogadro’s Number......Page 65
Periods and Groups......Page 67
Metals and Nonmetals......Page 68
Molecules......Page 70
Cations and Anions with Noble-Gas Structures......Page 75
Polyatomic Ions......Page 76
Ions......Page 77
Ionic Compounds......Page 78
Binary Molecular Compounds......Page 80
Acids......Page 81
Beyond the Classroom: Ethyl Alcohol and the Law......Page 83
Summary Problem......Page 84
Questions and Problems......Page 85
3 Mass Relations in Chemistry; Stoichiometry......Page 90
Mole-Gram Conversions......Page 91
Moles in Solution; Molarity......Page 93
Percent Composition from Formula......Page 98
Simplest Formula from Chemical Analysis......Page 100
Molecular Formula from Simplest Formula......Page 102
Writing and Balancing Chemical Equations......Page 103
Mass Relations from Equations......Page 105
Limiting Reactant and Theoretical Yield......Page 108
Experimental Yield; Percent Yield......Page 111
Beyond the Classroom: Hydrates......Page 112
Key Terms......Page 113
Questions and Problems......Page 114
4 Reactions in Aqueous Solution......Page 120
Solubility of Ionic Compounds......Page 121
Net Ionic Equations......Page 123
Stoichiometry......Page 124
4.2 Acid-Base Reactions......Page 126
Strong and Weak Acids and Bases......Page 127
Equations for Acid-Base Reactions......Page 128
Acid-Base Titrations......Page 130
4.3 Oxidation-Reduction Reactions......Page 133
Oxidation Number......Page 135
Balancing Half-Equations (Oxidation or Reduction)......Page 137
Balancing Redox Equations......Page 139
The Human Side: Svante August Arrhenius......Page 134
Beyond the Classroom: Reversible Color Changes......Page 142
Key Terms......Page 143
Questions and Problems......Page 144
5 Gases......Page 150
Pressure......Page 151
5.2 The Ideal Gas Law......Page 153
Final and Initial State Problems......Page 155
Calculation of P, V, n, or T......Page 157
Molar Mass and Density......Page 158
5.4 Stoichiometry of Gaseous Reactions......Page 161
The Human Side: Amadeo Avogadro......Page 165
Wet Gases; Partial Pressure of Water......Page 167
Partial Pressure and Mole Fraction......Page 168
Molecular Model......Page 170
Average Speed, u......Page 171
Effusion of Gases; Graham’s Law......Page 173
Distribution of Molecular Speeds......Page 175
5.7 Real Gases......Page 176
Particle Volume......Page 177
Beyond the Classroom: Measurement of Blood Pressure......Page 178
Summary Problem......Page 179
Questions and Problems......Page 180
6 Electronic Structure and the Periodic Table......Page 185
The Wave Nature of Light: Wavelength and Frequency......Page 186
The Particle Nature of Light; Photon Energies......Page 189
Atomic Spectra......Page 190
6.2 The Hydrogen Atom......Page 191
Bohr Model......Page 192
Quantum Mechanical Model......Page 193
Second Quantum Number,ℓ; Sublevels (s, p, d, f)......Page 195
Fourth Quantum Number, ms; Electron Spin......Page 196
Pauli Exclusion Principle......Page 197
6.4 Atomic Orbitals; Shapes and Sizes......Page 198
Electron Configuration from Sublevel Energies......Page 199
Filling of Sublevels and the Periodic Table......Page 201
The Human Side: Glenn Theodore Seaborg......Page 203
6.6 Orbital Diagrams of Atoms......Page 204
6.7 Electron Arrangements in Monatomic Ions......Page 206
Transition Metal Cations......Page 207
Atomic Radius......Page 209
Ionic Radius......Page 211
Ionization Energy......Page 212
Electronegativity......Page 213
Beyond the Classroom: Why Do Lobsters Turn Red When Cooked?......Page 214
Key Equations......Page 215
Questions and Problems......Page 216
7 Covalent Bonding......Page 220
7.1 Lewis Structures; The Octet Rule......Page 221
Writing Lewis Structures......Page 223
Resonance Forms......Page 225
Formal Charge......Page 227
Exceptions to the Octet Rule: Electron-Deficient Molecules......Page 228
Exceptions to the Octet Rule: Expanded Octets......Page 229
The Human Side: Gilbert Newton Lewis......Page 230
Ideal Geometries with Two to Six Electron Pairs on the Central Atom......Page 232
Effect of Unshared Pairs on Molecular Geometry......Page 234
Multiple Bonds......Page 236
Polar and Nonpolar Molecules......Page 239
7.4 Atomic Orbitals; Hybridization......Page 243
Hybrid Orbitals: sp, sp², sp³, sp³d, sp³d²......Page 244
Multiple Bonds......Page 246
Sigma and Pi Bonds......Page 247
Beyond the Classroom: The Noble Gases......Page 249
Key Terms......Page 250
Questions and Problems......Page 251
8 Thermochemistry......Page 255
State Properties......Page 256
Magnitude of Heat Flow......Page 257
Coffee-Cup Calorimeter......Page 260
Bomb Calorimeter......Page 261
8.3 Enthalpy......Page 263
8.4 Thermochemical Equations......Page 264
Rules of Thermochemistry......Page 265
Meaning of ΔH°f......Page 270
Calculation of ΔH°......Page 272
8.6 Bond Enthalpy......Page 276
8.7 The First Law of Thermodynamics......Page 278
ΔH  Versus ΔE......Page 280
Beyond the Classroom: Energy Balance in the Human Body......Page 282
Key Equations......Page 283
Questions and Problems......Page 284
9 Liquids and Solids......Page 289
9.2 Liquid-Vapor Equilibrium......Page 290
Vapor Pressure......Page 291
Vapor Pressure Versus Temperature......Page 294
Boiling Point......Page 295
Critical Temperature and Pressure......Page 296
9.3 Phase Diagrams......Page 297
Melting Point......Page 299
9.4 Molecular Substances; Intermolecular Forces......Page 300
Dispersion (London) Forces......Page 301
Dipole Forces......Page 302
Hydrogen Bonds......Page 303
Network Covalent Solids......Page 307
Ionic Solids......Page 309
Metals......Page 310
Metals......Page 312
The Human Side: Dorothy Crowfoot Hodgkin......Page 316
Beyond the Classroom: Supercritical Carbon Dioxide......Page 318
Summary Problem......Page 319
Questions and Problems......Page 320
10 Solutions......Page 325
Molarity (M)......Page 326
Mass Percent; Parts per Million; Parts per Billion......Page 328
Conversions Between Concentration Units......Page 330
Solute-Solvent Interactions......Page 334
Effect of Temperature on Solubility......Page 335
Effect of Pressure on Solubility......Page 337
10.3 Colligative Properties of Nonelectrolytes......Page 338
Vapor Pressure Lowering......Page 339
Boiling Point Elevation and Freezing Point Lowering......Page 340
Osmotic Pressure......Page 343
Determination of Molar Masses from Colligative Properties......Page 345
10.4 Colligative Properties of Electrolytes......Page 348
Beyond the Classroom: Maple Syrup......Page 351
Summary Problem......Page 352
Questions and Problems......Page 353
11 Rate of Reaction......Page 358
11.1 Meaning of Reaction Rate......Page 359
Measurement of Rate......Page 361
Rate Expression and Rate Constant......Page 362
Order of Reaction Involving a Single Reactant......Page 363
Order of Reaction with More Than One Reactant......Page 365
First-Order Reactions......Page 368
Zero- and Second-Order Reactions......Page 372
Collision Model; Activation Energy......Page 375
Transition-State Model; Activation Energy Diagrams......Page 377
11.5 Reaction Rate and Temperature......Page 378
The Arrhenius Equation......Page 379
Two-Point Equation Relating k and T......Page 380
Heterogeneous Catalysis......Page 382
Homogeneous Catalysis......Page 383
Enzymes......Page 384
Elementary Steps......Page 385
Deducing a Rate Expression from a Proposed Mechanism......Page 386
Elimination of Intermediates......Page 387
Beyond the Classroom: The Ozone Story......Page 389
Summary Problem......Page 390
Questions and Problems......Page 391
12 Gaseous Chemical Equilibrium......Page 400
12.1 The N2O4–N02 Equilibrium System......Page 401
Changing the Chemical Equation......Page 404
Adding Chemical Equations......Page 405
Heterogeneous Equilibria......Page 407
12.3 Determination of K......Page 409
Direction of Reaction; the Reaction Quotient (Q)......Page 412
Extent of Reaction; Equilibrium Partial Pressures......Page 414
Adding or Removing a Gaseous Species......Page 417
Compression or Expansion......Page 419
Change in Temperature......Page 420
Beyond the Classroom: An Industrial Application of Gaseous Equilibrium......Page 423
Key Terms......Page 424
Questions and Problems......Page 425
13 Acids and Bases......Page 431
13.1 Brønsted-Lowry Acid-Base Model......Page 432
13.2 The Ion Product of Water......Page 433
13.3 pH and pOH......Page 434
pH of Strong Acids and Strong Bases......Page 436
Measuring pH......Page 439
13.4 Weak Acids and Their Equilibrium Constants......Page 440
The Equilibrium Constant for a Weak Acid......Page 441
Calculation of [H+] in a Water Solution of a Weak Acid......Page 445
13.5 Weak Bases and Their Equilibrium Constants......Page 449
The Equilibrium Constant for a Weak Base......Page 450
Calculation of [OH-] in a Water Solution of a Weak Base......Page 451
Relation Between Ka and Kb......Page 452
Cations: Weak Acids or Spectator Ions?......Page 454
Salts: Acidic, Basic, or Neutral?......Page 455
13.7 Extending the Concept of Acids and Bases: The Lewis Model......Page 456
Beyond the Classroom: Organic Acids and Bases......Page 458
Key Concepts......Page 459
Questions and Problems......Page 460
14 Equilibria in Acid-Base Solutions......Page 465
14.1 Buffers......Page 466
Determination of [H+] in a Buffer System......Page 467
Choosing a Buffer System......Page 469
Effect of Added H+ or OH- on Buffer Systems......Page 474
Buffer Capacity and Buffer Range......Page 476
14.2 Acid-Base Indicators......Page 477
Strong Acid–Strong Base......Page 480
Weak Acid–Strong Base......Page 483
Strong Acid–Weak Base......Page 486
Titration of Diprotic Acids......Page 488
Summary......Page 489
Beyond the Classroom: Acid Rain......Page 490
Summary Problem......Page 491
Questions and Problems......Page 492
15.1 Complex Ion Equilibria; Formation Constant (Kf)......Page 497
Ksp Expression......Page 501
Ksp and the Equilibrium Concentrations of Ions......Page 502
Ksp and Water Solubility......Page 503
Ksp and the Common Ion Effect......Page 507
Ksp and Precipitate Formation......Page 509
Selective Precipitation......Page 511
15.4 Dissolving Precipitates......Page 513
Complex Formation......Page 516
Beyond the Classroom: Qualitative Analysis......Page 519
Key Terms......Page 520
Questions and Problems......Page 521
16 Spontaneity of Reaction......Page 526
The Energy Factor......Page 527
The Randomness Factor......Page 528
16.2 Entropy, S......Page 529
Standard Molar Entropies......Page 530
ΔS° for Reactions......Page 532
16.3 Free Energy, G......Page 533
Relation Among ΔG, ΔH, and ΔS......Page 534
16.4 Standard Free Energy Change, ΔG°......Page 535
Calculation of ΔG° at 25°C; Free Energies of Formation......Page 537
Calculation of ΔG° at Other Temperatures......Page 539
Temperature......Page 540
Pressure and Concentration......Page 542
16.6 The Free Energy Change and the Equilibrium Constant......Page 544
16.7 Additivity of Free Energy Changes; Coupled Reactions......Page 546
Beyond the Classroom: Rubber Elasticity: An Entropic Phenomenon......Page 548
Key Concepts......Page 549
Questions and Problems......Page 550
17 Electrochemistry......Page 556
The Zn-Cu²+ Cell......Page 557
Other Salt Bridge Cells......Page 559
E°red and E°ox......Page 561
Strength of Oxidizing and Reducing Agents......Page 562
Spontaneity of Redox Reactions......Page 565
E° and K......Page 568
17.4 Effect of Concentration on Voltage......Page 570
Nernst Equation......Page 571
Use of the Nernst Equation to Determine Ion Concentrations......Page 573
17.5 Electrolytic Cells......Page 574
Quantitative Relationships......Page 575
Cell Reactions (Water Solution)......Page 578
Electrolysis of Aqueous NaCl......Page 579
Primary (Nonrechargeable) Voltaic Cells......Page 580
The Human Side: Michael Faraday......Page 581
Fuel Cells......Page 583
Beyond the Classroom: Fuel Cells: The Next Step in Chemical-to-Electrical-Energy Conversion?......Page 584
Summary Problem......Page 586
Questions and Problems......Page 587
18 Nuclear Reactions......Page 593
18.1 Nuclear Stability......Page 594
18.2 Radioactivity......Page 595
Mode of Decay......Page 596
Bombardment Reactions......Page 598
Applications......Page 599
18.3 Rate of Radioactive Decay......Page 601
Age of Organic Material......Page 603
18.4 Mass-Energy Relations......Page 605
Nuclear Binding Energy......Page 607
The Fission Process (235/92U)......Page 609
Nuclear Reactors......Page 610
18.6 Nuclear Fusion......Page 612
Beyond the Classroom: Biological Effects of Radiation......Page 614
Summary Problem......Page 615
Questions and Problems......Page 616
19 Complex Ions......Page 620
19.1 Composition of Complex Ions......Page 621
Charges of Complexes......Page 622
Ligands; Chelating Agents......Page 623
Coordination Number......Page 624
Complex Cations and Neutral Complexes......Page 625
Coordination Compounds......Page 626
Coordination Number = 4......Page 627
Geometric Isomerism......Page 628
19.4 Electronic Structure of Complex Ions......Page 631
The Human Side: Alfred Werner......Page 632
Octahedral Complexes......Page 633
Color......Page 635
Beyond the Classroom: Chelates: Natural and Synthetic......Page 637
Questions and Problems......Page 639
20 Chemistry of the Metals......Page 642
Chloride Ores: Na from NaCl......Page 643
Oxide Ores: AI from A2O3, Fe from Fe2O3......Page 645
Sulfide Ores: Cu from Cu2S......Page 647
20.2 Reactions of the Alkali and Alkaline Earth Metals......Page 649
Reaction with Hydrogen......Page 650
Reaction with Oxygen......Page 651
Reactions of the Transition Metals with Oxygen......Page 653
Reaction of Transition Metals with Acids......Page 654
Equilibria Between Different Cations of a Transition Metal......Page 656
Oxoanions of the Transition Metals (Cr4²-, Cr2O7²-), MnO4-)......Page 657
Beyond the Classroom: Essential Metals in Nutrition......Page 659
Key Terms......Page 660
Questions and Problems......Page 661
21 Chemistry of the Nonmetals......Page 663
Chemical Reactivity......Page 664
Occurrence and Preparation......Page 667
Ammonia, NH3......Page 668
Hydrogen Sulfide, H2S......Page 669
Hydrogen Peroxide......Page 670
Hydrogen Fluoride and Hydrogen Chloride......Page 671
21.3 Oxygen Compounds of Nonmetals......Page 672
Molecular Structures of Nonmetal Oxides......Page 673
Reactions of Nonmetal Oxides with Water......Page 675
Acid Strength......Page 676
Oxidizing and Reducing Strength......Page 678
Nitric Acid, HNO3......Page 680
Sulfuric Acid, H2SO4......Page 681
Beyond the Classroom: Arsenic and Selenium......Page 683
Summary Problem......Page 684
Questions and Problems......Page 685
22 Organic Chemistry......Page 688
22.1 Saturated Hydrocarbons: Alkanes......Page 689
Nomenclature......Page 691
Sources and Uses of Alkanes......Page 693
Alkenes......Page 695
22.3 Aromatic Hydrocarbons and Their Derivatives......Page 697
Derivatives of Benzene......Page 698
Condensed Ring Structures......Page 699
Alcohols and Ethers......Page 700
Aldehydes and Ketones......Page 702
Carboxylic Acids and Esters......Page 704
Amines......Page 706
22.5 Isomerism in Organic Compounds......Page 708
Geometric (cis-trans) Isomers......Page 709
Optical Isomers......Page 710
22.6 Organic Reactions......Page 713
Elimination and Condensation Reactions......Page 714
Beyond the Classroom: Cholesterol......Page 715
Summary Problem......Page 717
Questions and Problems......Page 718
23 Organic Polymers, Natural and Synthetic......Page 721
Polyethylene......Page 722
Polyvinyl Chloride......Page 724
23.2 Synthetic Condensation Polymers......Page 725
Polyesters......Page 726
Polyamides......Page 727
23.3 Carbohydrates......Page 728
Glucose......Page 729
Maltose and Sucrose......Page 730
Starch......Page 731
23.4 Proteins......Page 732
α-Amino Acids......Page 733
Beyond the Classroom: DNA Fingerprinting......Page 740
Key Concepts......Page 741
Questions and Problems......Page 742
1 Units, Constants, and Reference Data......Page 745
2 Properties of the Elements......Page 751
3 Exponents and Logarithms......Page 753
4 Molecular Orbitals......Page 758
5 Answers to Even-Numbered and Challenge Questions and Problems......Page 764
INDEX/Glossary......Page 785
Conversion Factors......Page 805
Table of Atomic Masses......Page 806