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Volumetric Karl Fischer Titration

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Volumetric Karl Fischer Titration

Cosimo A. De Caro
Albert Aichert
Mettler-Toledo GmbH, Analytical
Switezrland
Karl Fischer Titration
Volumetric & Coulometric Karl Fischer Titration

Volumetric Karl Fischer

Iodine is added by burette during titration.
Water as a relevant component: 100 ppm - 100 %

- +

Coulometric Karl Fischer

Iodine is generated electrochemically during titration.
Water in trace amounts: 1 ppm - 5 %

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Karl Fischer Titration
Karl Fischer Reaction

Two step reaction

1. SO2 + RN + CH3OH  (RNH)SO3CH3

Methylsulfite

2. (RNH)SO3CH3 + H2O + I2 + 2 RN  (RNH)SO4CH3 + 2 (RNH)I

Methylsulfate

Iodine (I2) reacts with water 1:1

The solvent (methanol, CH3OH) is involved in the reaction.

50 % of the solvent must be methanol.

A suitable base (RN) keeps the pH value between 5 – 7

In the past: Pyridine now: Imidazole

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Karl Fischer Reaction
Optimum pH range: pH 5 - 7

log k

4
side reactions
optimal
2

slow
0
pH
2 4 6 8 10

The base imidazole keeps the pH in the range of 5 – 7

Pyridine is not the ideal base; pH of 4 – 5.

3
Karl Fischer Titrator
Volumetric Karl Fischer Titrator DL31/DL38

Titrant bottle

Waste

Burette

Solvent
Titrant

Titration cell

4
Air humidity
Air humidity, the big enemy of KF titration

0.5 - 3 mg water / 10 mL air

 Tropical countries: Air conditioning

 Well sealed titration cell
 Conditioning of the titration stand
 Protect:
- titration stand
- titrant
- waste and solvent
- from air humidity

5
Air humidity
Air humidity, the big enemy of KF titration

The titration stand is not 100 % tight

against air humidity.

Drift determination

The drift is the amount of water entering

into the titration stand per minute.
1 - 20 µg H20 / minute
Automatic drift compensation in the result
calculation.

6
Reagents
One - component reagent
Titrant: I2, SO2 and imidazole dissolved
in methanol and diethylene glycol
monoethylether
Solvent: Methanol

Two - component reagent

Titrant: I2 and methanol
Solvent: SO2, imidazole and methanol

 faster reaction
 Increased chemical stability
 more expensive

7
Reagents Concentration
Titrant concentration

KF titrant concentrations:
 1, 2 and 5 mg H2O/mL
 Fresh titrant: 10% higher concentration!

Titrant concentration not stable over time:

 Air humidity
 Chemical reaction (one component)

Check titrant concentration using a

reference material (standardization)

8
Reagents Standardization
Standardization

Standardization materials
 Water 100 %
 Disodium tartrate dihydrate 15.66 %
 Certified standards:
Water Standard 10 10.0 mg/g
Water Standard 1 1.0 mg/g
 Standardization with pure water is very difficult,
due to the very small sample size (10 – 30 mg).
 Low solubility of sodium tartrate in KF solvent:
max. 0.15 g in 40 mL methanol
max. 0.05 g in 40 mL ethanol

9
Reagents Standardization
Standardization: Tips and hints

 Every day, at least every week.

 Before standardization, rinse thoroughly the
burette tubes.
 Minimum concentration for:
- KF Titrant 5 mg/mL: 4 mg/mL
- KF Titrant 2 mg/mL: 1.5 mg/mL
Below these concentrations the KF
titrator does not work optimally (too
long titration times).

10
Resolution & Detection Limit
Volumetric Karl Fischer Titration

Resolution of burette: 10’000 steps

Detection limit : 50 x Resolution
Burette size: 5 mL

Titrant: 5 mg H20/mL
Resolution: 2.5 µg H20/step
Detection limit: 125 µg H20
For 5 g sample: 25 ppm

Titrant: 2 mg H20/mL
Resolution: 1 µg H20/step
Detection limit: 50 µg H20
For 5 g sample: 10 ppm

11
Repeatability
Volumetric Karl Fischer Titration

srel: relative standard deviation

100 %

10 %
Water content

srel < 0.5 %

1%

1000 ppm
srel 5 - 0.5 %
100 ppm
srel > 5 %
10 ppm
Not suitable for volumetry
1 ppm
12
Sample size
Volumetric Karl Fischer Titration

srel %
6
110 ppm
5
330 ppm
4
720 ppm
3

0
0.25 0.5 1.0 2.0 3.0 5.0 g sample
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Side Reactions
Reaction with methanol (CH3OH) + 1 H 2O

 Ketones, R1-C=O-R2, and aldehydes (R1-C=O-H) react with methanol

forming a ketal (acetal) and additional water :

Solution: Use special KF reagents for ketones/aldehydes

 Esterification:
Carboxylic acids (R-COOH) reacts under presence of strong acids (i.e.
sulfuric acid) with methanol (CH3OH) forming an ester (R-O-CO-CH3) and
additional water.
Solution: Neutralize the sample using a suitable base (imidazole)

14
Side Reactions
Reaction with iodine + 1 H 2O

 Iodine, I2, reacts with the following substances leading to the formation of
additional water:
- Oxides
- Hydroxides
- Carbonates
- Amines
- Ascorbic acid
- Mercaptans, etc.

Solution: External extraction, drying oven

15
Side Reactions
Reaction with water - 1 H2O

 Bisulfite addition:
Ketones and aldehydes react with sulphur dioxide, water and a base.

Solution: Fast titration: pre-dispensing 90% of titrant consumption

16
 Summary - Important Points

 System tightness: Check carefully

 Ambient moisture: Drift determination
 Stability of titrant: Standardization
 Side reactions: Check literature
 Free water only: Sample preparation

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