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Water determination by Karl Fischer Reagent (KF)

The titrimetric determination of water by the Karl Fischer method depends on the reaction that takes place quantitatively between water and a reagent consisting of sulfur dioxide and iodine in anhydrous pyridine and usually methanol. The reaction is carried out in a suitable solvent such as methanol or acetic acid.



Simple Reaction : Water against KF Reagent (Karl Fischer reagent)


ROH The solvent is generally methanol.

Methanol is the common solvent used as media.

  • When analysing Aldehydes and ketones, do not use methanol as a media. these compounds reacts with methanol to form additional water.
  • Number of iodines is equivalent to number water molecules in the reaction of iodine consumption.
  • KF degrades itself with atmospheric air and moisture, since the oxidation happening to sulfur dioxide. so that the standardisation of KF should be done frequently (Daily once).
  • Each ml of KF can neutralise (here react to consume) 5-6 mg of water. This will be exactly known by standardisation of KF with DST (Disodium tartrate dihydrate) or Water.
  • Commercially KF reagents available in two types with respect to concentration.
  1. 2 mg/ ml
  2. 5 mg/ml

Calibration of KF Apparatus as per USP<921>

  1. Water or DST can be used for KF standardisation, 
  2. While testing, the KF Consumption should be at least 30% of burette volume, this condition is for the purpose of accurate result, 
  3. Precision & accuracy of the water standard or DST can be verified

Standardisation of KF Reagent :
Weigh the DST( previously dried for 3 hours at 105 degrees) about 0.2 g and titrate with KF.

Formula: 


This 0.1566 comes from ratio of molecular weight of water divided by DST molecular weight.       


👉This standardisation can be done with water (Take pure water only)

Formula :

Here 0.1566 is not involved, since we are standardizing with water. so water molecular wt divided by water molecular wt. gives 1.

Note :
Take the sample to consume at least 10-30% of the burette volume so as to get accurate and reproducible results.



Second advanced method for lower levels of Water determination in the range of 5 ppm to 5.0%.




  • This method is called water content by Coulometry.
  • Here there is no Burette. The KF Reagent it self act as a generator of iodine in the vessel containing two platinum electrodes.
  • The reagent (KF for Coulometry) contains iodine in the form of Iodine Ion.
  • This iodine Ion oxidise to get free iodine which reacts with water.
  • No need to change the reagent for each sample.

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