The Karl Fischer titration is used in many different ways following its publication in 1935 and further applications are continually being explored. At the present time we are experiencing another phase of expansion, as shown by the development of new titration equipment and new reagents. KF equipment increasingly incorporates microprocessors which enable the course of a titration to be programmed thus sim­ plifying the titration. Coulometric titrators allow water determinations in the micro­ gram-range: the KF titration has become a micro-method. The new pyridine-free re­ agents make its application significantly more pleasant and open up further possibili­ ties on account of their accuracy. To make the approach to Karl Fischer titrations easier, we have summarized the present knowledge in this monograph and we have complemented it with our own studies and practical experience. As this book should remain "readable", we have tried to keep the fundamentals to a minimum. Historical developments are only mentioned if they seem to be necessary for understanding the KF reaction. The ap­ plications are described more fully. Specific details which may interest a particular reader can be found in the original publications cited. The referenced literature is in chronological order as the year of publication may also prove informative. Thus, [6902] for example denotes 69 for 1969 being the year of publication and 02 is a non-recurring progressive number. The referenced litera­ ture includes summaries which we hope will be of help to find the "right" publica­ tion easily.

Inhalt

1 Karl Fischer.- 2 The Karl Fischer Reaction.- 2.1 Stoichiometry.- 2.1.1 The Effect of the Solvent.- 2.1.2 The Effect of the Water Concentration.- 2.2 Kinetics.- 2.3 Own Investigations.- 2.3.1 The Stoichiometry in Presence of Various Amines.- 2.3.2 The Alcohol-Sulphur Dioxide-Water System.- 2.4 The Karl Fischer Equation.- 3 Titration Techniques.- 3.1 Titrations Using a One-Component Reagent.- 3.2 Titrations Using a Two-Component Reagent.- 3.3 Coulometric Determination.- 3.4 Back Titration.- 3.5 Titrations at Different Temperatures.- 3.6 Continuous Determinations.- 3.7 Indication.- 3.7.1 Visual Indication.- 3.7.2 Instrumental Indication.- 4 Reagent Solutions.- 4.1 Reagent Solutions for Volumetric Titrations.- 4.2 Reagent Solutions for Coulometry.- 4.3 Stability of Solutions.- 4.4 Preparation of Solutions.- 4.5 Standardization of Titre.- 4.5.1 Standardization Using Solid Hydrates.- 4.5.2 Standardization Using Water.- 4.5.3 Stardardization Using Alcohol-Water-Mixtures.- 5 Equipment.- 5.1 Equipment for Volumetric Analysis.- 5.1.1 Simple Titration Set-Ups.- 5.1.2 Multipurpose Titration Equipment.- 5.1.3 Karl Fischer Titrators.- 5.2 Equipment for Coulometry.- 6 Application and Sources of Error.- 6.1 Working Medium.- 6.2 The pH.- 6.3 Side Reactions.- 6.4 Atmospheric Moisture.- 6.5 Indication.- 6.6 Sample Handling.- 6.6.1 Taking Samples and Sample Storage.- 6.6.2 Administration of Samples.- 6.6.3 Liquids.- 6.6.4 Solids.- 6.6.5 Gases.- 6.7 Safety Precautions.- 7 Organic Compounds.- 7.1 Hydrocarbons.- 7.2 Halogenated Hydrocarbons.- 7.3 Alcohols and Phenols.- 7.4 Ethers.- 7.5 Aldehydes and Ketones.- 7.6 Acids, Esters and Salts.- 7.7 Nitrogen-Containing Compounds.- 7.7.1 Amines and N-Heterocycles.- 7.7.2 Amides.- 7.7.3 Nitriles and Cyanohydrins.- 7.7.4 Hydrazine Derivatives.- 7.7.5 Other Nitrogen Compounds.- 7.8 Sulphur Compounds.- 8 Inorganic Compounds.- 8.1 Halides.- 8.2 Oxides, Hydroxides and Peroxides.- 8.3 Sulphur Compounds.- 8.4 Selenium and Tellurium Compounds.- 8.5 Nitrogen Compounds.- 8.6 Phosphorus Compounds.- 8.7 Arsenic and Antimony Compounds.- 8.8 Carbonates, Bicarbonates.- 8.9 Silicon Compounds.- 8.10 Boron Compounds.- 9 Foodstuffs.- 9.1 Handling Samples.- 9.2 Titration Techniques.- 9.3 Carbohydrates.- 9.3.1 Sugars and Sugar Products.- 9.3.2 Starch, Dextrins, Pectins, Flour.- 9.4 Fats.- 9.5 High-Protein Foods.- 9.6 Various Foodstuffs.- 9.6.1 Fruit Juices, Alcoholic Beverages.- 9.6.2 Mayonnaise.- 9.6.3 Baby Food.- 9.6.4 Coffee, Instant Coffee.- 9.6.5 Egg Powder.- 9.6.6 Pudding Powder.- 9.6.7 Cocoa Powder, Cocoa Beans.- 9.6.8 Chocolate.- 9.6.9 Almonds, Hazelnuts.- 9.6.10 Marzipan.- 9.6.11 Pastries.- 9.6.12 Pasta.- 9.6.13 Grain.- 9.6.14 Dried Vegetables, Dried Fruit.- 9.6.15 Meat and Meat Products.- 10 Technical Products, Natural Products.- 10.1 Technical Gases.- 10.2 Liquid Products of Mineral Oil.- 10.3 Insulating Oils, Lubricating Oils and Greases.- 10.4 Plastics.- 10.5 Ion Exchange Resins.- 10.6 Cellulose, Paper, Wood.- 10.7 Insulating Paper.- 10.8 Surfactants.- 10.9 Cigarette Smoke Condensate.- 10.10 Paints and Varnishes.- 10.11 Fertilizers.- 10.12 Cement.- 10.13 Minerals.- Literature.- Author Index.