Contents 3 STRUCTURE AND STEREOCHEMISTRY OF ALKANES 83 3-1 Classification of Hydrocarbons(Review)83 3-2 Molecular Formulas of Alkanes 84 3-3 Nomenclature of Alkanes 85 Summary:Rules for Naming Alkanes 90 anes 93 1 s of Alkanes 9 e100 ations of Higher 3-10 Cycloalkanes 102 3-11 cis-trans Isomerism in Cycloalkanes 105 3-12 Stabilities of Cycloalkanes:Ring Strain 105 3-13 Cyclohexane Conformations 109 roblem-Soving Strategy:Drawing Chair 3-14 Conformations of Monosubstituted Cyclohexanes I13 3-15 Conformations of Disubstituted Cyclohexanes 116 Problem-Solving trateg:cis 3-16 Bicyclic Molecules 119 Chapter 3 Glossary 121 Study Problems 124 4 THE STUDY OF CHEMICAL REACTIONS 127 4-1 Introduction 127 4-2 Chlorination of Methane 127 4-3 The Free-Radical Chain Reaction 128 Key Mechanism:Free-Radical Halogenation 130 4-4 Equilibrium Constants and Free Energy 132 Enthalpy and Entropy 135 Bond-Dissociation Enthalpies 136 Enthalpy Cha Activation eeuation /39 K Temperature Dependence 4-10 Transition States 142 4-11 Rates of Multistep Reactions 144 4-12 Temperature Dependence of Halogenation 145 4-13 Selectivity in Halogenation 146 4-14 The Hammond Postulate 151 Strategy:Proposing Reaction 4-15 Radical Inhibitors 155 4-16 Reactive Intermediates 156 Summary:Reactive Intermediates 162 Chapter 4 Glossary 162 Study Problems 1653 STRUCTURE AND STEREOCHEMISTRY OF ALKANES 83 3-1 Classification of Hydrocarbons (Review) 83 3-2 Molecular Formulas of Alkanes 84 3-3 Nomenclature of Alkanes 85 Summary: Rules for Naming Alkanes 90 3-4 Physical Properties of Alkanes 91 3-5 Uses and Sources of Alkanes 93 3-6 Reactions of Alkanes 95 3-7 Structure and Conformations of Alkanes 96 3-8 Conformations of Butane 100 3-9 Conformations of Higher Alkanes 102 3-10 Cycloalkanes 102 3-11 cis-trans Isomerism in Cycloalkanes 105 3-12 Stabilities of Cycloalkanes; Ring Strain 105 3-13 Cyclohexane Conformations 109 Problem-Solving Strategy: Drawing Chair Conformations 112 3-14 Conformations of Monosubstituted Cyclohexanes 113 3-15 Conformations ofDisubstituted Cyclohexanes 116 Problem-Solving Strategy: Recognizing cis and trans Isomers 118 3-16 Bicyclic Molecules 119 Chapter 3 Glossary 121 Study Problems 124 4 THE STUDY OF CHEMICAL REACTIONS 127 4-1 Introduction 127 4-2 Chlorination of Methane 127 4-3 The Free-Radical Chain Reaction 128 Key Mechanism: Free-Radical Halogenation 130 4-4 Equilibrium Constants and Free Energy 132 4-5 Enthalpy and Entropy 135 4-6 Bond-Dissociation Enthalpies 136 4-7 Enthalpy Changes in Chlorination 137 4-8 Kinetics and the Rate Equation 139 4-9 Activation Energy and the Temperature Dependence of Rates 141 4-10 Transition States 142 4-11 Rates of Multistep Reactions 144 4-12 Temperature Dependence of Halogenation 145 4-13 Selectivity in Halogenation 146 4-14 The Hammond Postulate 151 Problem-Solving Strategy: Proposing Reaction Mechanisms 153 4-15 Radical Inhibitors 155 4-16 Reactive Intermediates 156 Summary: Reactive Intermediates 162 Chapter 4 Glossary 162 Study Problems 165 Contents vii