Analytical Chemistry of Organic Halogen Compounds

Preface

Chapter I Properties, Preparation and Reactions of the Halogens and of Organic Halogen Compounds

I. The Properties of the Halogens


1. Physical Properties


2. Chemical Properties

II. Main characteristics of Organic Halogen Compounds


1. Fluorine Compounds


2. Chlorine Compounds


3. Bromine Compounds


4. Iodine Compounds

III. Preparation of Organic Chlorine, Bromine and Iodine Compounds


1. Addition Reactions with Unsaturated Aliphatic Compounds


2. Halogenation by Substitution

IV. Preparation of Organic Fluorine Compounds


1. Fluorination of Aliphatic Compounds


2. Fluorination of Aromatic Compounds


3. Fluorination of Heterocyclic Compounds

V. Reactions of Organic Halogen Compounds


1. Types of Reactions


2. Reactivity of Halogen Compounds in Substitution Reactions


3. Reactivity of Halogen Compounds in Elimination Reactions


4. Behavior of Organic Halogen Compounds in Elimination Reactions


5. Halogen Exchange Processes


6. Reactions of Organic Fluorine Compounds

Chapter II Methods for the Detection of Halogens in Organic Compounds

I. General Concepts

II. Decomposition Methods


1. Alkali Metal Fusion


2. Decomposition with a Mixture of Magnesium Metal and Potassium Carbonate


3. Decomposition with Silver Permanganate


4. Carius Decomposition

III. Reactions Suitable for Non-selective Detection of Chloride, Bromide and Iodide Ions


1. Beilstein Test


2. Detection by Means of Halogen-Specific Gas Chromatographic Detectors

IV. Reactions Suitable for Specific Detection of Halide Ions


1. Detection of Chloride Ions


2. Detection of Bromide Ions


3. Detection of Iodide Ions


4. Detection of Halide Ions in the Presence of One Another


5. Detection of Fluoride Ions

V. Reactions and Methods Suitable for Direct Detection of Organic Halogen Compounds

VI. Analysis of Organic Halogen Compounds on the Basis of Their Derivatives

VII. Instrumental Methods

VIII. Reactions Suitable for Determination of the Position of the Halogen Atom in a Molecule

References 82

Chapter III Methods for the Determination of Chlorine, Bromine and Iodine in Organic Compounds

I. Methods of Analysis


1. Tools and Techniques in Gravimetric Microanalysis


2. Tools and Techniques in Titrimetric Microanalysis


3. Spectrophotometry Methods


4. Other Methods

II. Methods for the Determination of Chloride, Bromide and Iodide Ions


1. Chloride Ions


2. Bromide Ions


3. Iodide Ions

III. Methods for the Liberation of the Chlorine, Bromine and Iodine Content of Organic Compounds


1. Hydrolysis of Halogens in Aqueous or Organic Solutions


2. Decomposition of Organic Compounds with Acids or Oxidizing Acid Mixtures


3. Decomposition by Solids in Melts


4. Combustion Methods

IV. Some Methods for the Determination of the Chlorine, Bromine and Iodine Content of Organic Compounds


1. Determination of Chlorine and Bromine in Organic Compounds by Wet Decomposition


2. Determination of the Chlorine Content of Polyvinyl Chloride and Other Polymers Containing Chlorine, by Wet Decomposition


3. Oxidative Decomposition of Organic Halogen Compounds in the Parr Bomb, on the Semi-micro Scale


4. Combustion of Organic Chlorine, Bromine and Iodine Compounds in a Fast Stream of Oxygen, in an Empty Tube


5. Determination of Chlorine, Bromine and Iodine after Oxygen Flask Combustion on the Micro Scale

References

Chapter IV Analysis of Organic Fluorine Compounds

I. Methods for the Determination of Fluoride Ions


1. Gravimetric Methods


2. Titrimetric Methods


3. Colorimetric and Spectrophotometric Methods


4. Other Instrumental Analytical Techniques

II. Pretreatment of Organic Compounds before Determination of the Fluorine Content


1. Decomposition by Aqueous or Alkaline Hydrolysis and by Alkali Metals


2. Oxidative or Reductive Decomposition at High Temperatures


3. Decomposition with Oxidizing Gases

III. Methods Suitable for the Separation of Fluoride Ions from Other Substances, Including Interfering Ions

IV. Detailed Descriptions of Some Methods Suitable for the Determination of Fluorine in Organic Compounds


1. Semi-micro Determination of Fluoride Ions as Lead Chloride Fluoride after Fusion with Sodium or Potassium


2. Micro Titration of Fluoride Ions with Thorium Nitrate (Methylthymol Blue Indicator)


3. Determination of Fluorine, after Combustion in an Oxygen Atmosphere, by Potentiometric Titration


4. Spectrophotometric Methods using Lanthanum-Alizarin Fluorine Blue

References

Chapter V Ultramicro Chemical Methods for the Determination of the Halogen Content of Organic Compounds

I. General Review of the Methods


1. Ultramicro Balances


2. Apparatus for Titrimetric Analysis


3. Reagents and Solutions


4. Spectrophotometric and other Methods


5. Decomposition Methods

II. Determination Methods


1. Chloride Ions


2. Bromide Ions


3. Iodide Ions


4. Fluoride Ions

III. Methods for the Ultramicro Determination of the Halogen Content of Organic Compounds


1. Combustion of Organic Halogen Compounds by the Method Suggested by Belcher


2. Determination of Chloride Ions


3. Iodimetric Determination of Bromide Ions


4. Determination of Iodine


5. Spectrophotometric Determination of Fluoride Ions after Oxygen Flask Combustion

References

Chapter VI Qualitative and Quantitative Investigation of Organic Halogen Compounds Based on the Different Reactivities of the Halogens

I. Qualitative Methods


1. Reactions with Silver Nitrate in Aqueous Solution


2. Reactions with Ethanolic Silver Nitrate Solution


3. Reactions of Organic Halogen Compounds with Acetonic Sodium Iodide Solution

II. Quantitative Methods

References

Chapter VII Interfering Effects of Halogens; Their Elimination in the Determination of Other Elements

I. Determination of Carbon and Hydrogen

II. Determination of Nitrogen

III. Determination of Oxygen

IV. Determination of Sulfur

V. Determination of Other Elements

References

Chapter VIII Physical Constants of Organic Halogen Compounds of General Pharmaceutical and Industrial Importance

Formula Index

Subject Index