1Matter-Its Properties and Measurement

I-I Properties of Matter I1-2 Classification of Matter 21-3 The Scientific Method 31-4 The Need for Measurement 4 ,1-5 The English and Metric Systems of Measurement 4

1-6 SI Units 61-7 Density 71-8 Temperature 81-9 Problem Solving-The Conversion Factor (Factor-Label) Method 8

1-10 Significant Figures 13Summary, 15 Learning Objectives, 15 Some New Terms, 16Exercises, 16 -Additional Exercises, .19 Self- Test Questions, 20

21Development of the Atomic Theory

2-1 Dalto~'s Atomic Theory 212-2 Cathode Rays 252-3 Canal Rays (:Positive Rays) 272-4 X Rays 282-5 Radioactivity 29..2-6 The Nuclear Atom 302-7 Isotopes 312"8 Protons and Neutrons 322-9 A Summary of the Properties of Fundamental Particles 32

2-10 Chemical Elements 332-11 Atomic Weights 342-12 Postscript: Do Atoms Exist? 36Summary, 37 Learning Objectives, 37 Some New Terms, 37Exercises,38 Additional Exercises,!41 Self-Test Questions, 4l

vii

~

Stoichiometry I: Elements and Compounds

3-1 Avogadro's Number and the Concept of the Mole 433-2 Some Illustrative Examples Using the Mole Concept 443-3 Chemical Compounds 463-4 Chen1ica.l Nomenclature .483-5 Composition of Chemical Compounds 533-6 Analytical Chemistry 55Summary, 58 Learning Objectives, 58 Some New Terms, 59Exercises. 59 Additional Exercises. 61 Self- Test Questions-, 62

63

74

Stoichiometry II: Chemical Reactions

4-1 Experimental Evidence for Chemical Reactions 634-2 The Chemical Equation 644-3 Quantitative Significance of the Chemical Equation 674-4 Chemical Reactions in Solutions 704-5 Some Complexities in the Stoichiometry of Chemical Reactions4-6 Inclustrial Chemistry 77Summary, 80 Learning Objectives, 81 Some New Terms, 81Exercises. 82 Additional Exercises. 85 Self- Test Questions, 87

5 88Gases

5-1 Properties of a Gas 885-2 Gas Pressure 895-3 The Simple Gas Laws 925-4 The Gas Laws and Development of the Atomic Theory5-5 The Ideal Gas Equation 975-6 Molecular Weight Determination 99 -5-7 Gas Densities 1005-8 Gases in Chemical Reactions 1005-9 Mixtures of Gases 1025-10 The Kinetic Molecular Theory of Gases 1065-11 Nonideal Gases 1105-12 Postscript: The Atmosphere 111Summary, 113 Learning Objectives, 114 Some New Terms, 114Exercif;e~. 115 Additional Exercises. 118 Self- Test Questions, 119

12Thermochemistry .

6-1 Work and Heat 1216-2 Some Terminology 1246-3 The First Law of Thermodynamics 1256-4 Applications of the First Law of Thermodynamics to Chemical,

Reactions 1266-5 Relationships Involving j).H 1306-6 Standard Enthalpies of Formation 1326- 7 Sources and Uses of Energy 134Summary, 137 Learning Objectives, 137 Some New Terms, 137Exercises, 138 Additional Exercises, 141 Self- Test Questions. 142

~

Contents

Electrons in Atoms

7-1 Electromagnetic Radiation 1447-2 Atomic Spectra 1477-3 Quantum Theory 1497-4 The BohrAtom 1517-5 Wave-Pdrticle Duality 1547-6 The Uncertainty Principle 1557-7 Wave Mechanics 1567-8 Electron Orbitals and Quantum Numbers 1587-9 Electron "Spin"-A Fourth Quantum Number 160

7-10 Many-Electron Atoms 1617-11 Electron Configurations 1627-12 Electron Configura'tions of the Elements 163Summary, 166 Learning Objectives, 166 Some New Terms, 167Exercises, 167 Additional Exercises, 170 Self- Test Questions, 170

172Atomic Properties and the Periodic Table

8-1 On the Idea of Order 1728-2 Periodic Law and the Periodic Table 1728-3 A Modern Periodic Table-The Long Form 1758-4 Electron Configurations and the Periodic Table 1768-5 Metals and Nonmetals 1788-6 Atomic Radius 1808-7 Ionization Energy (Ionization Potential) 1838-8 Electron Affinity 1858-9 Electronegativity 1858-10 Magnetic Properties 1868-11 An Introduction to Descriptive Chemistry 187Summary, 191 Learning Objectives, 191 Some New Terms, 192Exercises, 192 Additional Exercises, 194 Self- Test Quesilons, 195

196

196

Chemical Bonding I: Basic Concepts

9-1 The Importance of Electrons in Chemical Bonding9-2 Ionic Bonding 1989-3 Covalent Bonding 2009-4 Covalent Lewis Structures-Some Examples 20 19-5 Covalent Bonding in Polyatomic Ions 2049-6 Resonance 2059-7 Failure of the Octet Rule 2069-8 Molecular Shapes 2099-9 Bond Energies and Bond Distances 2159-10 Partial Ionic Character of Covalent Bonds 2179-11 Oxidation States 221Summary, 222 Learning Objectives, 223 Some New Terms, 223Exercises. 224 Additional Exercises, 227 Self- Test Questions, 227

229Chemical Bonding II: Additional Aspects

10-1 The Valence Bond Method 23010- 2 Hybridization of Orbitals 23110-3 Multiple Covalent Bonds 23610-4 Molecular Orbital Theory 238

~

10-5 Bonding in the Benzene Molecule 24310-6 Other Structures with Delocalized Orbitals 24510-7 Bonding in Metals 24510-8 Semiconductors 248Summary, 248 Learning Objectives, 248 Some New Terms, 249Exercises, 249 i 'Additional Exerci~es, 251 Self- Test Questions. 251

253Liquids, Solids, and Intermolecular Forces

Il-l Comparison of the States of Matter 25311-2 Surface Tension 25411-3 Vaporization 25411-4 Some Calculations Involving Vapor Pressure and Related Concepts .25911-5 Transitions Involving Solids 26211-6 Phase Diagrams 26311-7 Evidence of Intermolecular Forces-Condensed States of the Noble

Gases 26511-8 Van der Waals Forces 26511-9 Hydrogen Bonds 26711-10 Network Covalent Solids 26911-11 The Ionic Bond as an Intermolecular Force 27111-12 Calculation of Lattice Energy-The Born-Haber Cycle 27211-13 Crystal Structures 27311-14 Ionic Crystal Structures 276Summary, 278 Learning Objectives, 279 Some New Terms, 280Exercises, 281 Additional Exercises, 284 Self- Test Questions. 285

286Mixtures

12-1 Homogeneous and Heterogeneous Mixtures 28612-2 Solution Concentration 28812-3 Some Illustrative Examples Utilizing Solution Concentrations 29012-4 Solubility Equilibrium 29112-5 Colligative Properties 29412-6 Theory of Electrolytic Dissociation 30112-7 lnterionic Attractions 30312-8 Colloidal Mixtures 304Summary, 307 Learning Objectives, 308 Some New Terms, 308Exercises, 309 Additional Exercises, 312 Self- Test Questions, 312

314

The Arrhenius

Chemical Kinetics

13-1 Rates of Chemical Reactions 31413-2 The Rate Lilw for Chemical Reactions 31713-3 Zero-Order Reactions 32013-4 First-Order Reactions 32013-5 Second-Order Reactions 32313-6 Collision Theory of Chemical Reactions 32513-7 Transition State Theory 32713.8 The Effect of Temperature on Reaction Rates-

Equation 32813-9 Catalysis 33013-10 Reaction Mechanisms 332Summary,335 Learning Objectives, 336 Some New Terms, 336Exercises. 337 Additional Exercises. 341 Self- Test Questions. 342

Principles of Chemical Equilibrium

14-1 The Condition of Chemical Equilibrium 34414-2 Additional Relationships Involving Equilibrium Constants14-3 Predicting the Direction and Extent of a Reaction 35114-4 EquilibI:ium Calculations-Some Illustrative Examples. 35214-5 The Eff~crof Temperature on Equilibrium 35714-6 Altering Equilibrium Conditions-Le Chatelier's Principle14-7 Kinetic Basis of the Equilibrium Constant 36014-8 The Ammonia Synthesis Reaction 362Summary,363 Learning Objectives, 364 Some,New Terms, 364Exercises. 365 Additional Exercises. 368 Self- Test Questions, 36'

147

1~R

~7

Thermodynamics, Spontaneous Change, and

193Solubility Equilibria in Aqueous Solutions

16-1 The Solubility Product Constant, Ksp 39316-2 Relationship Between Solubility and Ksp 39516-3 Precipitation Reactions 39816-4 Writing Net Ionic Equations 40116-5 Qualitative Analysis 40316-6 Precipitation Reactions in Quantitative Analysis 404Summary, 406 Learning Objectives, 407 Some New Terms, 407F.xl'.rcises. 407 Additional Exercises. 410 Self- Test Questions, 410

Acids and Bases

17-1 Acid-Base Theories 41217-2 Self-ionization (Autoionization) of Water 415

17-3 Strong Acids and Bases 41717-4 pH and pOH 41817-5 Weak Acids and Weak Bases 419

17-6 Polyprotic Acids 42317-7 Cations and Anions as Acids and Bases-Hydrolysis 425

17-8 Molecular Structure and Acid Strength 428Summary,432 Learning Objectives, 433 Some New Terms, 433Exercises. 434 Additional Exercises. 437 Self- Te~t. O'I~~t.i()n" 4,

EquilibrIum15-1 In Search of a Criterion for Spontaneous Change ~

15-2 Entropy and Disorder 37315-3 Free Energy and Spontaneous Change 375 .

15-4 Standard Free Energy Change, ~Go 37715-5 Free Energy and ~quilibrium 37815-6 (Relationship of ~Go to K 38015-7 The Third Law of Thermodynamics 383

15-8 Heat Engines 385Summary, 386 Learning Objectives, 387 Some New Terms, 387'Exercises. 388 Additional Exercise~, 390 Self- Test Q'lestions, 391

Additional Aspects of Equilibria in AqueousSolutions ,

18-1 The Common Ion Effect in Acid-Base Equilibria 43918-2 Butrer Solutions 44118-3 Acid-Base Indicators 44618.4 Neutralization Reactions and Titration Curves 44618.5 Solubility and pH 45118-6 H2& Equilibria Revisited-Precipitation and Solubilities of Metal

Sulfides 45318-7 Postscript: Equivalent Weight and Normality 455Summary, 458 Learning Objectives, 459 Some New Terms, 459Exercises, 460 Additional Exercises, 464 Self- Test Questions. 465'

Oxidation-Reduction and Electrochemistry

19-1 Oxidation-Reduction: Some Definitions 46619-2 Balancing Oxidation-Reduction Equation.s 46719-3 Measurement of Oxidation and Reduction Tendencies 47119-4 A New Criterion for Spontaneous Change 47519-5 Electrical Work and Free Energy 47719-6 Ecen as a Function of Concentrations 47819-7 Production of Electric Energy by Chemical Change 48219-8 Electrochemical Mechanism of Corrosion 48419-9 Electrolysis and Nonspontaneous Chemical Change 48519-10 Postscript: Equivalent Weight and Normality in

Oxidation-Reduction Reactions 489 ,Summary, 490 Learning Objectives, 490 Some New Terms, 491Exerci!;~s. 491 Arlditional Exercises. 494 Self- Test Questions, 495

The Chemistry of Selected Representative Elements

20-1 The Alkali (IA) and Alkaline Earth (IIA) Metals 49720-2 Boron and Aluminum 50120-3 The Halogen Elements (VIlA) 50320-4 Oxygen 50720-5 Sulfur 51120-6 The Nitrogen Family (VA) 51520-7 Additional Aspects of Nitrogen Chemistry 51620-8 Additional Aspects of Phosphorus Chemistry 51920.9 Silicon 521Summary,523 Learning Objectives, 524 Some New Terms, 524Exerci!;es. 525 -Additional Exercises. 527 Self- Test 'Questions, 528

529The Chemistry of Transition Elements

21-1 Some Properties of the Transition Elements 52921-2 An Overview of the First Transition Series 53121-3 Some Aspects of the Chemistry of Chromium 53521-4 Some Aspects of the Chemistry of the Iron Triad Elements 53721-5 Qualitative Analysis Revisited 541Summary, 543 Learning Objectives, 544 Some New Terms, 544Exercises, 545 Additional Exercises, 546 Self- Test Questions. 547

548Complex Ions and Coordination Compounds

22-1 VVerner's,Theory 54822-2 The CoordiR~tion Number 54922-3 Ligands 55022-4 Nome~clature 55122-5 Isamerism 553 .22-6 Bonding in Complex lons-Valence Bond Theory ,

22- 7 Inner and Outer Orbital Complexes 55622-8 Bonding in Complex lons-Crystal Field Theory 5cL22-9 Color of Complex Ions 55822-10 Equilibria Involving Complex Ions 55922-11 Some Kinetic Considerations 56222-12 Applications of Coordination ChemistrySummary, 566 Learning Objectives, 567Exercises. 568 Additional Exercises. 569

, 562

Some New Terms, 567

Self- Test Questions. 570

57

S74

Nuclear Chemistry

23-1 The Phenomenon of Radioactivity 57123-2 Naturally Occurring Radioactive Nuclides ?7323-3 Nuclear Reactions and Artificial Radioactivity23-4 Transuranium Elements 57523-5 Rate of Radioactive Decay 57623-6 Energetics of Nuclear Reactions 57923-7 Nuclear Stability 58123-8 Nuclear Fission 58323-9 Nuclear Fusion 58523-10 Effect of Radiation on Matter 58623-11 Applications of Radioisotopes 589Summary, 590 Learning Objectives, 591 Some New Terms, 592Exercises. 592 Additional Exercises. 594 Self- Test Questions. 595

596Organic Chemistry24-1 The Nature of Organic Compounds and Structure

24-2 Alkanes 60224-3 Alkenes and Alkynes 60524-4 Aromatic Hydrocarbons 60924-5 Alcohols, Phenols, and Ethers 61224-6 Aldehydes and Ketones 61424-7 Carboxylic Acids and Their Derivatives 61624-8 Amines 61824-9 Heterocyclic Compounds 61924-10 Synthesis of brganic Compounds 619Summary, 620 Learning Objectives, 621 Some New Terms, 621Exercises. 622 -'\.dditional Exercises, 625 Self- Test Ohestions, 626

627Chemistry of the Living State

25-1 Structure and Composition of the Cell 62725-2 Principal Constituents of the Cell 62725-3 Biochemical Reactivity 64425-4 The Nucleic Acids 651Summary, 654 Learning Objectives, 655 Some New Terms, 655Fy,,1'ri~,,~ I\~I\ At1t1itinn"l Fy,,1'ri~p~ I\~R ~plf- Tp~t ()11P~tinn~ "~Q

Natural Resources, the Environment, and Synthetic

Materials

26-1 Occurrence of the Elements 66026-2 The Atlnosphere as a Natural Resource 66126-3 Atmospheric Pollution 664'26-4 The Oceans as a Natural Resource 66826-5 The Water Environment 66926-6 Water Pollution 67226-7 Metals 67426-8 Some Raw Materials for the Inorganic Chemical Industry 68226-9 Raw Materials for the Organic Chemical Industry 68826-10 Polymers 69126-11 Some Key Chemicals 695Summary,696 Learning Objectives, 698 Some New Terms, 698Exercises, 699 Additional Exercises, 701 Self- Test Questions, 702

Introduction to Qualitative Analysis .

27-1 Overview of Inorganic Qualitative Analysis 70327-2 Alternative Methods of Inorganic Qualitative Analysis 70627-3 The Practice of Inorganic Qualitative Analysis 70927-4 Techniques of Semimicro Qualitative Analysis 71227.5 Apparatus for Semimicro Qualitative Analysis 71527-6 Initial Investigation of the Sample for Cation Analysis 71927-7 The Plan of the Following Chapters 720Summary, 721 Learning Objectives, 721 Some New Terms, 721Exercises, 722

Cation Group 1: The Chloride Group

28-1 The Chemistry and Occurrence of the Metals of the Chloride Groupand Their Common Compounds 723

28-2 Precipitation of the Chloride Group 72528-3 Separation and Identification of Lead(Il) 72828-4 Separation and Identification of Mercury(l) 73128-5 Identification of Silver(l) 733Summary, 735 Learning Objectives, 735 Some New Terms, 735Exercises, 736 Additional Exercises. 738 Self-Test Questions. 738

Cation Group 2: The Hydrogen Sulfide Group

29-1 Precipitation by Sulfide Ion 73929-2 Precipitation of the Hydrogen Sulfide Group 743 .29-3 Separation of the Hydrogen Sulfide Group into Subgroups 74529-4 Separation and Identification of Mercury(lI} 74729-5 Separation and Identification of Lead(lI} 75029-6 The Chemistry and Occurrence of Some Metals of Subgroup 2A.

Bismuth, Copper, and Cadmium-and Their CommonCompounds 751

29-7 Separation and Identification of Bismuth(l11} 75329-8 Identification of Copper(lI} 75529-9 Identification of Cadmium(lI} 75529-10 Reprecipitation of Subgroup 2B-Arsenic, Tin, and Antimony

Ions 75R

Contents xv

29-11 The Chemistry and Occurrence of the Metals of Subgroup 2B-Arsenic, Tin, and Antimony-and Their Common Compounds

29-12 Separation and Identification of Arsenic Ions 76129-13 Identification-.of Tin Ions 76329-14 Identification of Antimony Ions 765Summary,766 Learning Objectives, 766 Some New Terms, 767EJ(ercises. 767 : .Additional Exercises, 769 Se1f-Test Questions, 769

770Cation Group 3: The Ammonium Sulfide Group

30-1 Separation of the Ammonium Sulfide Group 77030-2 The Chemistry an'd Occurrence of the Metals of Subgroup 3A

Manganese, Iron, Nickel, and Cobalt-and Their CommonCompounds 774

~v-.; The Identification of Manganese(lI) Ion and the Separation ofAmmonium Sulfide Group into Subgroups 776

I Separation and Identification of Iron Ion 778Identification of Nickel and Cobalt Ions 781

JULV The Chemistry and Occurrence of the Metals of Subgroup 3BAluminum, Chromium, and Zinc-and Their CommonCompounds 783

30-7 Separation and Identification of Aluminum(llI) 78430-8 Separation and Identification of Chromium Ion 78730-9 Identification of Zinc(lI) 789Summary,790 Learning Objectives, 790 Some New Terms,F.xercises. 791 Additional Exercises, 793 Self-Test Questions, 10

't1\.1

30-4

30-5

'21\ "

791

'7QA.

I 795Cation Group 4: The Carbonate Group

31-1 The Chemistry and Occurrence of the Metals of the CarbonateGroup-Barium, Strontium, Calcium, and Magnesium-and TheirCommon Compounds 795

31-2 Precipitation by Carbonate Ion and Flame Testing 79831-3 The Separation and Identjfication of Barium Ion 80231-4 The Separation and Identification of Strontium Ion 80631-5 The Separation and Identification of Calcium Ion 80831-6 The Identification of Magnesium Ion 810Summary,811 Learning Objectives, 812 Some New Terms, 812F.xercises. 812 Additional Exercises, 814 Self-Test Questions, 815

816

.~~f\t11"1'Ogl"1"f\1tn m,,;.

Cation Group 5: The Soluble Group32-1 The Chemistry and Occurrence of Sodium, Potassium, and

Ammonium Ions 81632-2 The Thermal Decomposition of Ammonium Ion and the

Identification of Sodium Ion 81732-3 The Identification of Potassium and Magnesium Ions 82132-4 The Identification of Ammonium Ion 823Summary, 825 Learning Objectives, 825 Some New Terms, 825Exercises. 825 Additional Exercises, 827 Se1f-Test Questions, 827

U~\J

~r- ~ -~~- "' '~,",J TVJ.a\,J.J.~ UJ.UUp CtllU lIlt

Barium Group

33-1 Detection and Removal of Cation Interference 82933-2 DetecJiop of Anion Group I: The Acid-Volatile Group 83133-3 The Chemistry, Occurrence, and Analysis of Carbonate Ion 83233-4 The Chemistry, Occurrence, and Analysis of Sulfite Ion 83633-5 The Chemistry, Occurrence, and Analysis of Thiosulfate Ion 83833-6 The Chemistry, Occurrence, and Analysis of Sulfide Ion 83933-7 The Chemistry, Occurrence, and Analysis of Nitrite Ion 84133-8 Detection of Anion Group 2: The Barium Group 84333-9 The Chemistry, Occurrence, and Analysis of Sulfate Ion 84533-10 The Chemistry, Occurrence, and Analysis of Chromate Ion 84633-11 The Chemistry, Occurrence, and Analysis of Phosphate Ion 84733-12 The Chemistry, Occurrence, and Analysis of Oxalate Ion 84933-13 The Chemistry, Occurrence, and Analysis of Borate Ion 850Summary, 852 Learning Objectives, 852 Some New Terms, 853Exercises, 853 Additional Exercises, 855 Self-Test Questions, 857

U.JI

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Group

34-1 The Detection of Anion Group 3: The Silver Group 85734-2 The Chemistry, Occurrence, and Analysis of Iodide Ion 85~34-3 The Chemistry, Occurrence, and Analysis of Thiocyanate Ion", 86134-4 The Chemistry, Occurrence, and Analysis of Bromide Ion 86234-5 The Chemistry, Occurrence, and Analysis of Chloride Ion 86434-6 The Chemistry, Occurrence, and Analysis of Nitrate.jon 86634- 7 The Chemistry, Occurrence, and Analysis of Acetate Ion 867Summary, 870 Learning Objectives, 870 Some New Terms, 870Exercises, 871 Additional Exercises, 873 Self-Test Questions, 873

U/"T--~~- .I ~ --~~-~. .~~'-' J " ~ .LV J.,", VJ.J.J.pVU.llU~

35-1 Qualitative Analysis of Alloys 87435-2 Dissolving Ionic Compounds 88135-3 Dissolving Acid-Insoluble Solids 88435-4 Planning an Analysis 889Summary, 892 Learning Objectives, 893 Some New Terms, ~~-Exercises, 893 Additional Exercises, 895 Self-Test Questions, 895

U.71

--r r ~~

Mathematical Operations

A-t Exponential Arithmetic 897A-2 Logarithms 898A-3 Algebraic Operations 899A-4 Graphs 903

v£~ £ ££)"..'"'".. ,",V~~'"""'J:.1l"

B-1 Velocity and Acceleration 904

B-2 Force and Work 904

/V"T

Contents xvii

B-3 Energy 905

B-4 Magnetism 905

B-5 Static EleGtricity 906

B-6 Current Electricity 906

B- 7 Electromagnetism 907

908SI Units

C-l SI Base Units 908C-2 SI Prefixes 908C-3 Derived SI Units 909C-4 Units to Be Discouraged or Abandoned 909C-5 Fundamental Constants 910

Thermodynamic Properties of Substances 9]

Electron Configurations of the Elements 913

Answers to Selected Exercises 916

Index 929