G E N E R A L C H E M I S T R Y

SSI» :

gl'*:;»

SECOND EDITION

IS'iP^Äiisiöpsfflli

^ ^ ; ^ # f e 3 ^ :

'OH N B. RUSSELL

Professor of Che mistry

Humboldt State University

• • • • • • • ' • • .

M c G R A W - H I L L , I h New York St. Louis San Francisco Auckland i Caracas Lisbon London Madrid Mexico Milar Montreal New Delhi Paris San Juan Singapore Sydney Tokyo Toronto

sB i l t l l i t lM

C O N T E N T S

Preface

CHAPTER 1 PRELIMINARIES AND PREMISES

1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8

Chemistry: What, Why, and How? Scientific methodology Matter Changes in matter Energy Numbers, their use and misuse Metrie units Solving numerical problems Summary Problems

CHAPTER 2 FORMULAS, EQUATIONS, AND STOICHIOMETRY

2-1 The microstrueture of matter 2-2 Chemical formulas 2-3 Atomic and other masses 2-4 The mole 2-5 Compound stoiehiometry 2-6 Chemical equations 2-7 Reaction stoiehiometry 2-8 Solution stoiehiometry 2-9 The mole: additional comments 2-10 Chemical nomenclature: a first look

Summary Problems

CHAPTER 3 THERMOCHEMISTRY

3-1 3-2 3-3 3-4 3-5

The first law of thermodynamics Heat and enthalpy Calorimetry Thermochemical equations The combustion of coal: a thermochemical ülustration Summary Problems

CONTENTS

CHAPTER 4 GASES

4-1 Variables used for describing gas behavior 4-2 Pressure-volume relationship: Boyle's law 4-3 Temperature effects: Charles' law 4-4 The ideal-gas law 4-5 Other properties of the ideal gas 4-6 Kinetic-molecular theory 4-7 Gas stoichiometry 4-8 Real gases

Summary Problems

111

112 115 121 127 132 140 145 149 155 156

CHAPTER 5

CHAPTER 6

THE ATOM

5-1 Early modeis of the atom 5-2 The nuclear atom 5-3 Atomic masses 5-4 Electrons in atoms

Summary Problems

ELECTRONS

6-1 The quantum-mechanical model and electronic energies 6-2 Waves and particles 6-3 Standing waves 6-4 The wavelike properties of electrons 6-5 Quantum numbers

Summary Problems

161

162 168 173 175 186 186

189

190 204 208 212 222 225 226

\

CHAPTER 7 CHEMICAL PERIODICITY

7-1 The discovery of the periodic law 7-2 Periodicity in electronic configurations 7-3 Periodicity in atomic properties 7-4 Periodicity in physical properties 7-5 Periodicity in chemical properties

Summary Problems

229

230 234 238 247 249 258 259

CHAPTER 8 CHEMICAL BONDING

8-1 8-2 8-3 8-4 8-5 8-6

Ionic bonding Covalent bonding Electronegativity Bond energies Electronic bookkeeping, part I: formal charges Electron-pair repulsion

263

264 275 285 290 293 296

CONTENTS

8-7 The polarity of molecules Summary Problems

302 306 309

CHAPTER 9 SOLIDS

9-1 Solids: some preliminary observations 9-2 X-ray diffraction 9-3 The crystal lattice 9-4 Close packing 9-5 Bonding and properties of solids 9-6 Lattice energy 9-7 Defects in crystals

Summary Problems

313

314 315 319 323 330 334 336 340 340

\

CHAPTER 10

CHAPTER 11

LIQUIDS AND CHANGES OF STATE

10-1 10-2 10-3 10-4 10-5 10-6 10-7

Liquids Equilibrium and vapor pressure The Variation of vapor pressure with temperature Solid-liquid equilibria Changes of State Equilibrium and Le Chätelier's principle Phase diagrams Summary Problems

SOLUTIONS

11-1 11-2 11-3 11-4 11-5 11-6

General properties of Solutions Types of Solutions Concentration units Solubility Colligative properties Electrolytes Summary Problems

345

346 348 352 358 360 364 371 374 375

379

380 380 382 386 398 412 421 422

R 1 2 AQUEOUS-SOLUTION REACTIONS

12-1 Acid-base reactions 12-2 Precipitation and complexation reactions 12-3 Net equations for aqueous-solution reactions 12-4 Electronic bookkeeping, part II: oxidation numbers 12-5 Electron-transfer reactions 12-6 Solution stoichiometry

Summary Problems

427

428 434 438 445 449 459 467 467

CHAPTER 13 CHEMICAL KINETICS 473

13-1 Reaction rates and mechanisms: a preview 13-2 The rate law 13-3 Collision theory 13-4 The activated complex 13-5 Reaction mechanisms: an introduction 13-6 Catalysis

Summary Problems

474 479 494 504 506 507 510 511

CHAPTER 14 CHEMICAL EQUILIBRIUM

14-1 Homogeneous chemical equilibria 14-2 The law of chemical equilibrium 14-3 Kinetics and equilibrium 14-4 Heterogeneous chemical equilibria 14-5 The Variation of K with temperature 14-6 Equilibrium calculations

Summary Problems

517

518 523 530 533 534 537 543 543

CHAPTER 15 AQUEOUS SOLUTIONS: ACID-BASE EQUILIBRIA

15-1 The dissociation of weak acids 15-2 The dissociation of weak bases 15-3 The dissociation of water 15-4 Hydrolysis 15-5 Acid-base indicators and titration 15-6 Buffers 15-7 Simultaneous acid-base equilibria

Summary Problems

549

550 560 565 569 578 589 593 597 599

CHAPTER 16 AQUEOUS SOLUTIONS: SOLUBIUTY AND COMPLEX-ION EQUILIBRIA 603

16-1 The solubility of ionic solids 604 16-2 Precipitation reactions 612 16-3 Complex-ion equilibria 615 16-4 Simultaneous equilibria 622

Summary 627 Problems 628

CHAPTER 17 CHEMICAL THERMODYNAMICS

17-1 The first law: a reconsideration 17-2 The second law 17-3 Gibbs free energy and spontaneous change 17-4 Changes in entropy and Gibbs free energy 17-5 Thermodynamics and equilibrium

Summary Problems

631

632 640 647 651 657 662 662

CHAPTER 18

CHAPTER 19

ELECTROCHEMISTRY

18-1 18-2 18-3 18-4 18-5 18-6

Galvanic cells Electrolytic cells Standard electrode potentials Free energy, cell voltage, and equilibrium The electrochemical measurement of pH Commercial galvanic cells Summary Problems

COVALENT BONDING

19-1 19-2 19-3

Valence-bond theory and orbital overlap Hybrid orbitals Molecular-orbital theory Summary Problems

667

668 676 688 694 700 704 708 708

713

714 717 727 739 740

CHAPTER 20

CHAPTER 21

THE NONMETALS

20-1 20-2 20-3 20-4 20-5 20-6 20-7 20-8 20-9

Inorganic nomenclature Hydrogen Oxygen Water The halogens The chalcogens, especially sulfur The group-VA nonmetals: nitrogen and phosphorus Carbon The noble gases Summary Problems

THE REPRESENTATIVE METALS AND METALLOIDS

21-1 21-2 21-3 21-4 21-5

The alkali metals The alkaline-earth metals The group-IIIA metals Other representative metals The metalloids

743

744 745 750 757 758 769 778 790 796 798 799

805

806 811 820 825 829

Summary Problems

839 840

CHAPTER 22 THE TRANSITION METALS

22-1 Electronic configurations 22-2 General properties 22-3 Complex ions: general structure and nomenclature 22-4 Bonding in complexes 22-5 The stereochemistry of complex ions

845

846 846 850 854 868

CONTENTS

22-6 Descriptive chemistry of selected transition elements Summary Problems

872 891 893

CHAPTER 23

CHAPTER 24

APPENDIXES

ORGANIC CHEMISTRY

23-1 23-2 23-3 23-4 23-5 23-6 23-7 23-8 23-9 23-10 23-11 23-12 23-13

Saturated hydrocarbons Unsaturated hydrocarbons Aromatic hydrocarbons Functional groups Alcohols Ethers Aldehydes Ketones Carboxylic acids Esters Amines Enantiomerism in organic Compounds Carbohydrates and proteins Summary Problems

NUCLEAR PROCESSES

24-1 24-2 24-3 24-4 24-5 24-6

Radioactivity The kinetics of nuclear decay Nuclear reactions Nuclear stability Fission, fusion, and nuclear binding energy Chemical applications of radioactivity Summary Problems

A. Glossary of Important Terms B. Units, Constants, and Conversion Equations

D.

E. F .

B- l . Units B-2. Physical Constants B-3. Conversion Equations Chemical Nomenclature C-l. Trivial Names C-2. Systematic Inorganic Nomenclature C-3. Systematic Organic Nomenclature Mathematical Operations D-l . Linear Equations and Their Graphs D-2. Quadratic Equations D-3. Logarithms Clark's Method of Writing Lewis Structures Vapor Pressure of Water

897

899 907 912 915 916 921 922 925 927 930 932 934 935 940 941

945

946 950 953 955 958 963 966 967

A-l A-13 A-13 A-14 A-14 A-15 A-15 A-15 A-21 A-24 A-24 A-24 A-25 A-26 A-28

CONTENTS

G. Selected Thermodynamic Properties at 25°C A-29 H. Equilibrium Constants at 25°C A-31

H- l . Dissociation Constants of Weak Acids A-31 H-2. Dissociation Constants of Weak Bases A-31 H-3. Solubility Products A-32

I. Standard Reduction Potentials at 25°C A-33 J . Answers to Selected Numerical Problems A-35

Index 1-1