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Journal (Karl Fischer)
Journal (Karl Fischer)
In a year 1935 a German scientist Karl Fischer published a method for determination of water content in
samples. This was a titrimetric method based on Bunsen reaction used for determination of sulfur dioxide
in aqueous solutions:
Karl Fischer discovered that if sulfur dioxide is added in the excess the same reaction can be used for water
determination by titration of the produced acids. His base of choice was pyridine which was allegedly “just
standing in the rack”. In his honor the titration is named Karl Fischer titration (KF titration for short).
In the following years both original stoichiometry and reagents were revised. Fischer presented the
reaction which gave incorrect molar ratio assuming aqueous Bunsen reaction in which methanol functions
only as a solvent.The error was corrected by Smith, Bryant and Mitchell who discovered that pyridine acts
only as a buffer substance, giving us the reaction which is used today:
The titration was conducted manually at first. The endpoint was signaled by persistence of brown color
from the added excess of iodine. This was not only slow, but also not suitable for colored samples.
Nowadays KF titration is automated and widely used for water determination in various industries.
There are two different techniques for water determination by Karl Fischer: Volumetric KF titration and
coulometric KF titration.
Volumetric determination is suitable for determination of water content down to 1% of water. The
sample is dissolved in KF Solvent (usually methanol based) and the iodine is added as a part of a KF Reagent
containing sulfur dioxide and iodine dissolved in pyridine and methanol. The endpoint is determined
potentiometrically.
Figure 1: Volumetric Karl Fischer titrator
Coulometric Karl Fischer analysis requires only one, iodide-containing, solution. Iodine needed for KF
reaction is produced by anodic oxidation of iodide from solution and the endpoint is detected
electrochemically. Coulometric determination is best suited for samples with less than 1% of water.
Reagents for Karl Fischer titration are available in a broad range, depending on the purpose and ecological
awareness of the user. Pyridine can be replaced with stronger base (and less smelly) imidazole, and
ethanol can be used instead of methanol as a more “green” choice of solvent. Different auxiliaries are
available, such as additives for fats and oils, reagents for determination of low water contents, solubilizers
for poorly soluble substances, and buffer solutions for strongly alkaline or strongly acidic samples.
Karl Fischer titration is widely used for direct analysis of water content in various industries, as a reliable
and robust method. In food industry it is used for water content determination in fruit juices, honey, flour,
noodles, chips, cocoa powder, in petroleum industry for all kinds of different oils, gasoline, kerosene, and
petroleum, in cosmetic industry for determination of water in shampoos, creams, lipstick, tooth paste, in
pharmaceutic industry for raw materials, active substances, lyophilized substrates, tablets, ointments,
oils. It is used for determination of water in silk, wool, wood, paper, and even in building materials such
as zeolite and cement.The list just goes on.
This is just the proof that with the right choice of technique and suitable reagents Karl Fischer titration
can be suitable for water content determination in almost all imaginable samples. It is no surprise that
this titration is a go to technique in any laboratory, in any industry.
REFERENCES:
https://www.chemistryworld.com/opinion/karl-fischers-titrator/5695.article
https://www.eurofins.com/biopharma-services/product-testing/services/biopharma-product-testing-
services/quality-control/raw-materials-and-excipient-testing/water-determination-by-karl-fischer/
http://www.wako-chem.co.jp/english/labchem/product/analytical/aquamicron/index.htm
https://www.mt.com/dam/MT-NA/KarlFischerHelpPage/KF_Chemicals.pdf
Disclaimer: The views expressed here are those of the author expressed in the