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ASTM D6304 Method for Determination of Water in Petroleum Products, Lubricating Oils, and Additives by Coulometric Karl Fischer Titration has three procedures (all coulometric) for determining water content. The procedures can be used based on the sample itself, known interactions, and/or equipment availability.
An aliquot is injected into the titration vessel of a coulometric Karl Fischer apparatus in which iodine for the Karl Fisher reaction is generated coulometrically at the anode. When all of the water has been titrated, excess iodine is detected by an electrometric end point detector and the titration is terminated.
Water content is determined by measuring the current needed for oxidation until the reaction is completed. Measuring cells for coulometric determination consist of anode and cathode compartments which can be separated by a diaphragm.
Karl Fischer titration is a widely used analytical method for quantifying water content in a variety of products. The fundamental principle behind it is based on the Bunsen Reaction between iodine and sulfur dioxide in an aqueous medium.
The Karl Fischer method determines only water and no other compounds because of the selective and stoichiometric reaction between the water in the sample and the iodine in the reagent. There are multiple different ways to release the water from the samples and determine the correct water content.
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The titration can be performed volumetrically or coulometrically. In the volumetric method a Karl Fischer solution containing iodine is added until the first trace of excess iodine is present. The amount of iodine converted is determined from the burette volume of the iodine-containing Karl Fischer solution.
Sodium Tartrate Dihydrate as Primary Standard for Karl Fischer Reagent | Analytical Chemistry.
The Karl Fischer titration is a moisture determination method specific for water and is suitable for samples with a high water content (titrimetry) and also for those with water content in the ppm range (coulometry).

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