Salts contain water in different kinds of bonding states: adherent moisture - enclosed water - crystal water. For determination of the total water content the substance must be completely dissolved. If the salt does not dissolve in methanol sufficiently, formamide can be added to the recipient vessel and/or titration carried out at 50 °C. If adherent moisture alone is of interest the dissolution of the sample must be prevented through addition of a non-polar solvent (e.g. chloroform) to the KF solvent. A good alternative for salts to the direct volumetric determination is often the Karl Fischer oven technique. Through slow heating of the sample it is hereby possible to differentiate among the various types of water bonding. For salts that cause disturbing side reactions in the KF solutions (e.g. carbonates, sulphites, borates) the KF oven technique is the method of choice. The same is also true for oxides and hydroxides. These alkaline compounds react with the weakly acidic KF solution resulting in the formation of water, which is erroneously detected as water during the titration. Aqueous inorganic acids and bases are titrated volumetrically. Since stoichiometry and reaction rate of the Karl Fischer reaction are influenced by the pH, sufficient buffering of the KF solution is a prerequisite for reproducible and accurate results. Optimum conditions are obtained in the neutral pH range (pH 4 - 8). Thus, the determination of acids is performed through the addition of Aquastar® buffer solution for strong acids, imidazole or a derivative of imidazole to the titration media. For the titration of bases the pH is adjusted by addition of Aquastar® buffer solution for strong bases, salicylic acid or benzoic acid. With particularly strong, highly concentrated acids the propensity for esterification in methanolic solutions should also be noted. In such cases external neutralisation in a methanol-free medium is necessary.
Magnesium chloride is only slightly soluble in common Karl Fischer reagents.
The addition of Formamide as solubiliser leads to a better solubility and reproducible results.
The indirect coulometric titration in combination with the Karl Fischer oven technique shows reproducible results at 250°C.
188005 Aquastar® - CombiTitrant 5 - One component reagent for volumetric Karl Fischer titration, 1 mL = approx. 5 mg water
30 mL 188009 Aquastar® - CombiMethanol - Solvent for volumetric Karl Fischer titration with one component reagents, max. 0.01 % water
20 mL 109684 Formamide - as solubiliser
Stirring time: 180 sec.
Default titration settings, e.g.:
I(pol) = 20 - 50 µA, U(EP) = 100 - 250 mV
Stop criterion: drift < 20 µL/min
The titration medium is first placed into the titration cell and titrated dry by means of the titrant. Then the sample is added from a weighing boat (exact sample weight determination by weighing of weighing boat before and after addition) and the titration is started. For complete extraction of the sample a stirring time of at least 180 seconds is recommended.