Karl Fischer titration

History:-

Karl Fisher as an imaginative person with an original mind , in 1927 he joined a company ;
there he specialized in petrochemistry. In 1945 he was professor of petrochemistry at Maryland
University in USA.

In his professional life he was just a versatile, imaginative and witty. His specialist field ;
deparcination of petroleum, separation of unsaturated compound analysis of paraffin, conditioning of
drilling muds, aluminium silicates cracking catalysts, determination of aromatics in white oils. He
became famous on account of a publication in “ Angewandle Chemie” 1935: Neues Verfahren Zur
mabanalytischen Bestimung Des Wassergehaltes Von Flussigkeiten and Festen Korpern.” This
“conjuring trick” of Karl Fischer promoted a whole generation of chemists to open up all the many
possibilities of application.

Karl Fischer Reagent

In 1935 Karl Fischer published the determination of water content which carries his name
and thus influenced developments in his field for several decades. He proposed a methanolic
solution of

Iodine 0.33 mol//

Sulphur dioxide 0.50 mol//
Pyridine 1.67 mol//

Karl Fischer reagent prepared by the action of SO2 and solution of iodine in a mixture of
anhydrous pyridine and anhydrous methanol water reacts with this reagent in two process. For
practical work the Karl Fischer reagent has been modified several times.
Now a days pyridine free Karl Fischer Reagent is available in market as pyridine is not
hygienic.

LABINDIA-AUTOMA TIC KARL fiSCHER TITRA TOR

INTRODUCTION:

Karl Fischer titration is said to be the most reliable method for the determination of
moisture content. Karl Fischer Reagent is required as titrant to determine the moisture
content within the Sample. The Moisture content is evaluated by relating the KF Volume
consumed for titration. Generally Karl Fischer reagent with concentration / Strength - 5 is
used. ( 1 ml. KF == 5 mg H2O) It is used in the quantitative analysis for moisture in solids,
liquids and gases. The results could be calculated as "concentration" or "percentage"(%) or
"ppm" of moisture in given sample.

.Specifications:

Control: Microcontroller based.

Burette: 5 ml or 10 ml capacity, interchangeable, with auto recognition. Burette resolution:
1/10000 for 10 ml and 1/5000 for 5 ml.
Filling time: < 20 sec. .
Principle: Karl Fischer method of volumetric water determination.
Measuring Range: 10 ug (titrant diluted to 1:5) to 500 mg.
Polarising Current Range: 1 uA to 80 uA in 8 steps - User selectable, method parameter
entry through keyboard.

....... mV range: :t 3200 mV.

. Accuracy: i: 1 mV.
. End point detection: Voltametric.
. Cut-off criteria: Delay or drift - user selectable.
. Results: mglml, % . ppm and on-line leak rate with cumulative titrant consumption. .
Keyboard: Alphanumeric splash water proof polyester soft keys.
. Display: 20 x 2 line backlighted, liquid crystal display (LCD).
. Sensor: Dual pin platinum electrode.
.. Sensor input: Through special TNC I BNC 12 x 4 mm banana connector.
. Stirrer: Magnetic capsule type, microcontrollor based speed control with digital
indication.
. Data Storage: Non-volatile memory.
. Method Storage: 50 methods with parameters.
. Input/Output peripheral interface: a) Parallel Port: 1 No. for printer.
b)Serial Port: 2 Nos. for Balance & PC.
. Report Format: Selection of various report formats: a) Method parameter. b)
Titration analysis report c) Titration analysis condensed report d) Statistics and online
leak rate report.
. Environmental Operating Conditions: a) Operation: Indoor. b) Temperature:
Ambient to 45 °C c) Relative Humidity: 5 to 90 % non-condensing.
. Power: 230 V AO:t 10 % ,50 Hz.
Features of KAFI :

Advanced Microcontroller based user-friendly

Four modes of titration: Neutralisation, Concentration, Percentage (%) and PPM.
Selectable report format, complying with GLP requirements: A) Report giving
titration parameter and result. B) Report of method parameters. C) Condensed
report of titration parameter and result. D) Statistics report for last 5 repeat run
analysis. Reports can be obtained even after resetting / power off / power failure
conditions.

Built-in standardisation procedure for Water/Sodium Tartrate complying with

USP 23/921.
End point delay up to 100 sec for slow moisture releasing samples.
Titration run can be started with last run parameters.

Aim – Determination of moisture in the given sample of lactic acid by Karl Fischer
method.

Chemicals:- Sample of lactic acid, pyridine free Karl Fischer reagent, Distilled water,
methanol AR [Analytical Reagent].

Instrument:- Labindia Automatic Karl Fischer Titrator.KAFI

Principle :-

When water containing sample is titrated with the Karl Fischer Reagent the water
reacts with iodine & form hydrogen iodide.
The other components of the reagent do not react with water nor HZ is formed in
reaction. They are miscible with reagent and do not cause precipitation of the complexes.
They will conduct an electric current due to hydrated salt.
After the water is neutralized completely, the excess of iodine remain in the
solution due to which flow of current stops immediately. This is known as dead stop end
point.
When excess of iodine is present in reagent it react with electrode with electrode
and the electrode depolarize it shows current flowing. Potential difference is required
0.80 mu. 1 ml anhydrous solvent is added to dissolve the sample. The sample is titrated
directly with Karl Fischer reagent.

Apparatus:- Labindia Automatic Karl Fischer Titrator.KAFI, Micro-syringe.

Conditions :

 The substance must dissolve in a suitable solvent or readily give up its water.
 It can not change the working pH of KF system
  It can not enter into a side reaction with component of KF system.

Reaction:

3RN + I2 + SO2 + H2O 2RNHI + RSO3N

(pyridine sulphur trioxide)

RNSO3 + CH3OH RN OSO2OCH3

H
(pyridine n-sulphonic acid)
Advantages
1)Potentiometric determination of water in poly ethers by the Karl Fischer method.
2) Determination of trace moisture in hydrogen chloride gas by Karl Fischer method
3)Determination of water by titration with coulometrically generated Karl Fischer reagent
4)Application of Karl Fischer water method to oxidants , reductants and amines
5) Water determination in hydrocarbons is simple by this method .
Procedure:

Determination for concentration by using Na-Tarturate and water. But we use

water only.

1. Conc. of water : -

Standardization of KF. Reagent. The whole cell assembly was washed with
distilled water & dried. About 40ml of methanol was then taken in the beaker &
about 10ml of distilled water to add to it. Then this solution was titrated with K.F.
reagent & the reading was noted.

Standardization of K.F.
Volume = 2.428 ml KF reagent for 10µL of water (10mg of water)
Concentration = 4.1186 mg/ml of KF.

2. For sample: -

Procedure

After standardization of K.F. reagent quickly add weighed quantity of (alcohol)

sample few ml of solution in the titration assembly. And titrate to the end point using
reagent.
The water content of the solution, in ml, is given by C & F. where ‘C’ is the
volume in ml of reagent used to titrate the solution & F is the water equivalence
factor.

Calculations: -

(A) For sample

% Moisture – R X F X 100
W

R = ml. of KF required for titration

F = Water equivalent of KF
W = Weight taken of the sample

In case KaR1 instrument we are getting direct results on the display. After feeding
particular method for moisture analysis.
e.g.
moisture in %, in ppm.
There is separate method for standardization of KF.

(B)

Determine the H2O content in sample

Parameter / conditions for Karl Fischer.

Mode – Method 1
Mode – concentration
Minimum dose – 10ml
Delay – 30sec
Current setting – 6(10A)
Stir time – 20 sec
Blank vol – 0.0ml
Sample name - water

Method – 2

 Mode – percentage %
 Minimum dose – off
 E.P. factor – 30
 Drift (l/mn) – 10
 Drift type – Final
 Current – 6 (16A)
 Stir time – 180 sec.
 Blank vol. – 0.1 ml