Professional Documents
Culture Documents
Karl-Fischer Titration
Karl-Fischer Titration
The process uses an organic base (B), sulphur dioxide, iodine and an
alcohol. The original Karl Fischer method used pyridine as organic base
and methanol as alcohol. Since then the reagents have been improved.
Nowadays Karl Fischer reagents are available which are less toxic (no more
pyridine but imidazole as organic base, ethanol instead of methanol) and
which provide a faster reaction.
During the titration, iodine is added to sample and the amount of iodine used
to consume all the water contained in the sample is measured.
Karl fischer titration apparatus
Karl fischer titration
Coulometric titration
Volumetric titration
Base(B):-Pyridine
Imidazole
Alcohol:-Methanol
Ethanol
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 ethanol 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
• Coulometric titrations
The amount of water contained in the samples should be small for two reasons:
Many samples can be titrated without needing to replace the Karl Fischer
reagent.
Short analysis times.
For these reasons, the sample should ideally contain between 100 and 1000 μg of
H2O. To ensure reliable results, the samples should contain at least 50 μg of H2O
as always small traces of water can enter into the titration cell.
• Hybrid titrations
The sample size should be such that the samples contain between
50 μg and 18 mg of H2O if the titer of the reagent is 2 mg/L
50 μg and 45 mg of H2O if the titer of the reagent is 5 mg/L
%Water(w/w)=B.R. F. 100
Wt.100