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CONTENTS

A Leak from a Buried Chlorine Pipe A 14,000-lb Liquid Leak 55

54

A Tank Car Leak at a Chlorine Packager 57 Brush Fire 59 Frequency and Magnitude of Chlorine Leaks

59

Production and Uses of Chlorine 62

Annual Production 62 End Uses of Chlorine 62 Help in Chlorine Emergencies

64

References 65

Chemistry of Aqueous Chlorine

Dissolution and Hydrolysis of Chlorine Dissociation of Hypochlorous Acid 74

68

Effect of pH and Temperature 74 Ionic Strength Effects 77

Chlorine Speciation in Concentrated Solutions Hypochlorite Solutions 82 Oxidation States of Chlorine 85 Free, Combined, and Available Chlorine 87 Chlorine and Nitrogenous Compounds 91

81

Nitrogenous Compounds in Water and Wastewater

92

Chlorination of Ammonia to Form Chloramines The Breakpoint Reaction 103 The Organic Nitrogen Problem 116

94

The Chemistry of Chlorine in Seawater

122

Effect of Bromide 123 Ionic Strength Effects 126 Bromamine Formation and Decay

127

Oxidation–Reduction Reactions of Chlorine Compounds

129

Fundamental Considerations 129 Practical Considerations 133

ORP Measurements 135 Practical Applications of ORP Measurements Reactions of Chlorine with Selected Constituents

139 141

Alkalinity 142 Arsenic 145 Carbon 145 Cyanide 146 Hydrogen Sulfide 146 Iron and Manganese 147

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