1 Atoms 1

1-1 Atoms and the Atomic Theory 1

1-2 Components of the Atom 2

The Human Side: John Dalton 3

1-3 Quantitative Properties of the Atom 5

1-4 Introduction to the Periodic Table 11

Beyond The Classroom: Mastering the Perigodic Table 14

Summary Problems 16

Questions and Problems 16



2 Electronic Structure and the Periodic Table 19

2-1 Light, Photon Energies, and Atomic Spectra 20

2-2 The Hydrogen Atom 25

2-3 Quantum Numbers 28

2-4 Atomic Orbitals; Shapes and Sizes 32

2-5 Electron Configurations in Atoms 33

The Human Side: Glenn Theodore Seaborg 37

2-6 Orbital Diagrams of Atoms 38

2-7 Electron Arrangements in Monatomic Ions 40

2-8 Periodic Trends in the Properties of Atoms 43

Beyond The Classroom: Why Do Lobsters Turn Red When Cooked 47

Summary Problems 49

Questions and Problems 49



3 Covalent Bonding 52

3-1 Lewis Structures; The Octet Rule 53

The Human Side: Gilbert Newton Lewis 62

3-2 Molecular Geometry 62

3-3 Polarity of Molecules 70

3-4 Atomic Orbitals; Hybridization 73

Beyond The Classroom: The Noble Gases 80

Summary Problems 81

Questions and Problems 81



4 Thermochemistry 85

4-1 Principles of Heat Flow 86

4-2 Measurement of Heat Flow; Calorimetry 90

4-3 Enthalpy 93

4-4 Thermochemical Equations 94

4-5 Enthalpies of Formation 100

4-6 Bond Enthalpy 105

4-7 The First Law of Thermodynamics 107

Beyond The Classroom: Energy Balance in the Human Body 111

Summary Problems 113

Questions and Problems 113



5 Spontaneity of Reaction 116

5-1 Spontaneous Processes 117

5-2 Entropy, S 119

5-3 Free Energy, G 123

The Human Side: J. Willard Gibbs 125

5-4 Standard Free Energy Change, G 125

5-5 Effect of Temperature, Pressure, and Concentration on Reaction Spontaneity 129

5-6 The Free Energy Change and the Equilibrium Constant 134

5-7 Additivity of Free Energy Changes; Coupled Reactions 135

Beyond The Classroom: Rubber Elasticity: An Entropic Phenomenon 137

Summary Problems 139

Questions and Problems 139



6 Gaseous Chemical Equilibrium 144

6-1 The N2O4NO2 Equilibrium System 145

6-2 The Equilibrium Constant Expression 148

6-3 Determination of K 153

6-4 Applications of the Equilibrium Constant 156

6-5 Effect of Changes in Conditions on an Equilibrium System 161

Beyond The Classroom: An Industrial Application of Gaseous Equilibrium 166

Summary Problems 168

Questions and Problems 169



7 Rate of Reaction 171

7-1 Meaning of Reaction Rate 171

7-2 Reaction Rate and Concentration 174

7-3 Reactant Concentration and Time 180

7-4 Models for Reaction Rate 186

The Human Side: Henry Eyring 189

7-5 Reaction Rate and Temperature 190

7-6 Catalysis 193

7-7 Reaction Mechanisms 195

Beyond The Classroom: The Ozone Story 199

Summary Problems 201

Questions and Problems 202



8 Liquids and Solids 206

8-1 Comparing Solids, Liquids, and Gases 206

8-2 Liquid-Vapor Equilibrium 207

8-3 Phase Diagrams 213

8-4 Molecular Substances; Intermolecular Forces 216

Beyond The Classroom: Supercritical Carbon Dioxide 222

Summary Problems 224

Questions and Problems 224



9 Solutions 227

9-1 Concentration Units 227

9-2 Principles of Solubility 236

9-3 Colligative Properties of Nonelectrolytes 241

9-4 Colligative Properties of Electrolytes 250

Beyond The Classroom: Maple Syrup 252

Summary Problems 254

Questions and Problems 254



10 Acids and Bases 257

10-1 Br nsted-Lowry Acid-Base Model 257

10-2 The Ion Product of Water 259

10-3 pH and pOH 259

10-4 Weak Acids and Their Equilibrium Constants 265

10-5 Weak Bases and Their Equilibrium Constants 274

10-6 Acid-Base Properties of Salt Solutions 278

10-7 Extending the Concept of Acids and Bases: The Lewis Model 281

Beyond The Classroom: Organic Acids and Bases 282

Summary Problems 285

Questions and Problems 285



11 Equilibria in Acid-Base Solutions 288

11-1 Buffers 288

11-2 Acid-Base Indicators 299

11-3 Acid-Base Titrations 302

Beyond The Classroom: Acid Rain 311

Summary Problems 313

Questions and Problems 313



12 Precipitation Equilibria 316

12-1 Solubility; Solubility Product Constant (Ksp) 316

12-2 Precipitate Formation 323

12-3 Dissolving Precipitates 327

Beyond The Classroom: Qualitative Analysis 331

Summary Problems 333

Questions and Problems 334



13 Electrochemistry 337

13-1 Oxidation-Reduction Reactions Revisited 338

13-2 Voltaic Cells 342

13-3 Standard Voltages 346

13-4 Relations Between E , DG , and K 353

13-5 Effect of Concentration on Voltage 355

Beyond The Classroom: Fuel Cells: The Next Step in Chemical-to-Electrical-Energy Conversion 359

Summary Problems 361

Questions and Problems 362



14 Complex Ions 366

14-1 Composition of Complex Ions 367

14-2 Naming Complex Ions and Coordination Compounds 371

14-3 Geometry of Complex Ions 373

14-4 Electronic Structure of Complex Ions 377

The Human Side: Alfred Werner 377

14-5 Complex Ion Equilibria; Formation Constant (Kf) 382

Beyond The Classroom: Chelates: Natural and Synthetic 384

Summary Problems 386

Questions and Problems 387



15 Nuclear Reactions 389

15-1 Nuclear Stability 389

15-2 Radioactivity 391

The Human Side: Marie and Pierre Curie with daughter Irene, at their home near Paris 397

15-3 Rate of Radioactive Decay 397

15-4 Mass-Energy Relations 400

15-5 Nuclear Fission 404

15-6 Nuclear Fusion 407

Beyond The Classroom: Biological Effects of Radiation 409

Summary Problems 410

Questions and Problems 410



Appendices

Appendix 1 Units, Constants and Reference Data 413

Appendix 2 Properties of the Elements 419

Appendix 3 Exponents and Logarithms 421

Appendix 4 Molecular Orbitals 426

Appendix 5 Answers to All Questions and Problems 431



Conversion Factors 443



Table of Atomic Masses 444



IUPAC Periodic Table of the Elements 445