Dear Bujji,

Karl Fischer titration is a classic titration method that uses coulometric or volumetric titration to determine trace amounts of water in a sample. It was invented in 1935 by the German chemist Karl Fischer.

Coulometric titration

The main compartment of the titration cell contains the anode solution plus the analyte. The anode solution consists of an alcohol (ROH), a base (B), SO2 and I2. A typical alcohol that may be used is methanol or diethylene glycol monoethyl ether, and a common base is imidazole. The titration cell also consists of a smaller compartment with a cathode immersed in the anode solution of the main compartment. The two compartments are separated by an ion-permeable membrane. The Pt anode generates I2 when current is provided through the electric circuit. The net reaction as shown below is oxidation of SO2 by I2. One mole of I2 is consumed for each mole of H2O. In other words, 2 moles of electrons are consumed per mole of water.

B·I2 + B·SO2 + B + H2O → 2BH+I− + BSO3

BSO3 + ROH → BH+ROSO3−

The end point is detected most commonly by a bipotentiometric method. A second pair of Pt electrodes are immersed in the anode solution. The detector circuit maintains a constant current between the two detector electrodes during titration. Prior to the equivalence point, the solution contains I− but little I2. At the equivalence point, excess I2 appears and an abrupt voltage drop marks the end point. The amount of charge needed to generate I2 and reach the end point can then be used to calculate the amount of water in the original sample.

Volumetric titration

The volumetric titration is based on the same principles as the coulometric titration except that the anode solution above now is used as the titrant solution. The titrant consists of an alcohol (ROH), base (B), SO2 and a known concentration of I2. Pyridine has been used as the base in this case.

One mole of I2 is consumed for each mole of H2O. The titration reaction proceeds as above, and the end point may be detected by a bipotentiometric method as described above.

References:

Fischer, Karl (1935). "Neues Verfahren zur maßanalytischen Bestimmung des Wassergehaltes von Flüssigkeiten und festen Körpern". Angew. Chem. 48 (26): 394–396. doi:10.1002/ange.19350482605.

http://www.astm.org/Standards/E203

Tavčar, E., Turk, E., Kreft, S. (2012). Simple Modification of Karl-Fischer Titration Method for Determination of Water Content in Colored Samples. Journal of Analytical Methods in Chemistry, Vol. 2012, Article ID 379724 http://www.hindawi.com/journals/jamc/2012/379724/

Hoping this will be helpful,

Rafik

Thank you sir.

I want to know about when i was analysis of highly alkaline base compound that effect to Karl Fischer tiration in about the water content in the compound