Karl

Fischer
Volumetric

Basic knowledge
at a glance

The most important points

Chemical fundamentals
Titrants
Concentration determination
Accuracy
The correct amount of sample
Sample addition, liquid
Sample addition, solid
Optimum control parameters
Termination parameters
Side reactions
Drying oven
Troubleshooting
 The most important
points

• Keep titration stand tightly sealed.

• Protect titration stand, solvent bottle and waste

bottle with molecular sieves or silica gel.

• Change silica gel and molecular sieves every

month.

• Silica gel can be regenerated at 150 °C, molecular

sieves at 300 °C.

• Perform a concentration determination daily.

• Perform a drift measurement several times a day

(if no online drift determination is available).

Instruments for the Karl Fischer

titration
Karl Fischer titrators
DL31 and DL38 (DL18 and DL35)

General titrators
DL53, DL55, DL58 with DV705 & KF option
(Memory card for Karl Fischer methods)

DL67, DL70ES, DL77 with DV705

 Theory

Chemical reaction

SO2 + RN + CH3OH → (RNH)SO3CH3

(RNH)SO3CH3 + H2O + I2
→ [RNH]SO4CH3 + 2[RNH]I

The solvent methanol is a reaction partner.

The ideal pH range for the Karl Fischer

reaction lies between 5 and 7.

A suitable buffer (imidazole)

keeps the pH at 5 – 7.

Below pH 5 slower reaction

Above pH 7 side reactions

Hence Acid samples (pH < 5)

➠ add buffer (imidazole).

Basic samples (pH > 7)

➠ add salicylic acid.

Water must be freely available

If this is not the case:
Sample – dissolve
– crush (mix, grind)
– extract
– heat, evaporate water

See Karl Fischer brochures

– Foods, beverages, cosmetics
– Chemicals, solvents, mineral oil
products, plastics
– Foldout «Method at a glance»
 Titrants

One-component titrants
Titrants:
Iodine, sulfur dioxide,
imidazole, methanol.

Solvent:
Methanol.

Advantage: Simple, favorably

priced.
All reactive components in
one solution.
Disadvantage: Titration speed
slower. Titrant not as stable.

Two-component titrants
Titrants:
Iodine, methanol.

Solvents:
Sulfur dioxide, imidazole,
methanol.

Advantage: High titration

speed. Titrant stable.
Disadvantage: Reactive
components distributed
between two solutions.

Special titrants & solvents

Methanol-free titrants and
solvents for aldehydes and
ketones.

Solvents for oils and fats.

Titrant concentration / water content

5 mg/mL: 1000 ppm – 100 %
2 mg/mL: < 1000 ppm
 Concentration
determination

Why?
The ingress of atmospheric moisture causes a
decrease in the titrant concentration.

When?
At least once a week, better every day.

When left to stand overnight, the titrant in the

dispensing tubing has a lower concentration than
that in the flask owing to the ingress of moisture
through the Teflon tubing.

Hence, before the concentration determination

expend 2 – 3 mL titrant or rinse burette.

How?
With di-sodium tartrate • 2 H2O

Sample weight: 0.05 – 0.12 g

The concentration determination is correct only if the
sodium tartrate has dissolved completely.
– Max. 0.12 g di-sodium tartrate dissolve in 40 mL
methanol.
– Use pure methanol for the concentration
determination. Di-sodium tartrate is insoluble in a
chloroform/methanol mixture.
The same applies to mixtures with decanol,
hexanol or toluene.

With water standard 10.0

Sample weight: 1.0 – 1.5 g
– Open ampoule.
– Rinse 10 mL syringe with approx. 1 mL standard.
– Fill 10 mL syringe with the entire ampoule
contents.
– Inject aliquots of approx. 1 mL and determine the
weight by backweighing.

With pure water

Sample weight: 0.01 – 0.04 g

The use of water for the concentration

determination requires practical experience to
obtain accurate, reproducible results!
Use a 10 or 20 µL syringe.
For weighing in (0.04 g sample), use a balance with
a resolution of ±0.1 mg.
 Accuracy

Resolution: 10 000 steps/burette

• For 5 mg/mL titrant: 2.5 mg H2O/step
• For 2 mg/mL titrant: 1 mg H2O/step

Accuracy: Determined with repeatability

Amount of sample versus srel

for different water contents
srel: Relative standard deviation [%]
6

5
110 ppm
330 ppm
4
720 ppm
3 1300 ppm

0
0.25 0.5 1 2 3 5
Sample weight [g]

Expected relative standard deviation

for different water contents
with optimum amount of sample and control
100%

10 %
srel < 0.5 %
1%

1000 ppm srel 1 – 0.5 %

100 ppm srel 1 – 5 %

srel > 5 %
10 ppm
not suitable
1 ppm
 Amount of sample

50 µg – 500 mg H2O/sample
optimum: 10 mg H2O/sample
for titrant 5 mg/mL

Determination of the amount of sample

Starting from the two optimum points or the
recommended range, the best possible amount of
sample can be determined as a function of the
expected water content. For this, the optimum point
is connected by a straight line to the expected water
content. The intersection point of this line with the
scale «Amount of sample» represents the best
possible amount of sample.

Water content Amount of sample Amount of water

100 % 1 µg

10 % 10 µg

1% 0.01 g 100 µg

0.1 g

1000 ppm 1g 1 mg

10 g

100 ppm 100 g 10 mg

10 ppm 100 mg

1 ppm 1000 mg

Example
Optimum water content: 10 mg H2O/sample
Expected water content: 5000 ppm
Optimum sample weight: 2g
Liquid samples

Fill a quarter of the syringe with

sample.

Pull up plunger.

Rinse syringe with sample by

shaking it.
Empty syringe and sample into
waste bottle.

Fill syringe with sample.

Wipe needle with paper towel.

Place syringe with sample on

the balance.

Tare to zero.

Starting titration method.

Press RUN.

Inject sample into titration cell,

either through the hole in the
three-hole adapter or through
a septum stopper.

Pull back plunger so that the

drop at the tip of the needle
flows back into the needle.
Otherwise, when the syringe is
removed the drop will adhere to
the septum.

Place syringe with sample

on balance and back weigh.

Enter weight on titrator or have

it transferred.

Start titration.
Solid samples

Wait until drift value is stable.

Weigh sample into weighing
boat.

Tare balance to zero.

Starting titration method.

Press RUN.

Add sample to titration cell.

Care
Sample must not adhere to the
electrode or the beaker wall!

Back weigh empty weighing

boat.

Enter weight on titrator or have

it transferred.

Start titration.
 Control parameters

Polarization current (Ipol) End point (EP)

1 µA 20 – 30 mV
5 µA 50 – 70 mV
10 µA 80 – 100 mV
20 µA 100 – 125 mV
30 µA 130 – 150 mV

Optimum control parameters (DL31/38)

quick and accurate
Ipol = 20 mA; EP = 100 mV
Rel. drift stop = 15 µg/min
Titrant ∆Vmax ∆Vmin ∆Vmax factor
µL µL %
One-component 4.0 0.5 100
Two-component 8.0 0.5 30
One-component for (Ipol = 20 µA; EP = 125 mV)
aldehydes & ketones 5.0 0.5 100
Two-component (Ipol = 10 µA; EP = 100 mV)
pyridin containing 5.0 0.5 40

High titration speed (DL31/38)

Accuracy lowered
Ipol = 20 µA; EP = 100 mV
Rel. drift stop = 30 µg/min
Titrant ∆Vmax ∆Vmin ∆Vmax factor
µL µL %
One-component 6.0 0.5 100
Two-component 10.0 0.5 25

Optimum control parameters

(DL53/55/58)
Ipol = 10 µA; EP = 50 mV
Delay time = 15 s
Titrant Vmin Control band
mL mV
One-component 0.02 50
Two-component 0.01 250
One-component for
aldehydes & ketones 0.02 50
 Te r m i n a t i o n p a r a m e t e r s

Delay time
The titration is terminated
when the measured value
E [mV]
drops below the endpoint for
the predefined time.
Typical delay time:
15 seconds

EP

15 s
t [s]

Absolute drift stop

Drift
Drift[µg/min]
[mg/min] The titration is terminated
when the current drift is less
than the predefined absolute
drift value.
Typical value: 30 µg/min

abs.Driftstopp
abs. drift stop
µg/min
30µg/min
==30
t [s]

Relative drift stop

The titration is terminated
when the current drift is less
Drift
Drift[µg/min]
[mg/min] than the sum of the initial drift
and predefined relative drift.
Typical value: 20 µg/min

rel.Driftstopp
rel. drift stop
==20 20µg/min
µg/min

Initial drift
Anfangsdrift
t [s]
 Side reactions

Reaction with methanol

Aldehydes and ketones react with methanol to form
an acetal or ketal and water:
➠ water content too high!
Use special reagents for aldehydes and
ketones (methanol-free).

Strong acids react with methanol to form an ester

and water:
➠ water content too high!
Neutralize acids with a base,
e.g. imidazole

Reaction with iodine

Some compounds are oxidized by iodine resulting in
an anomalously high iodine consumption:
➠ water content too high!

Such compounds include the following:

Arsenites (AsO2–)
Ascorbic acid
Bicarbonates (HCO3–)
Boric acid (H3BO3, HBO2)
Boron trioxide (B2O3)
Tetraborates (B4O72–)
Carbonates (CO32–)
Copper(I) salts
Disulfites (S2O52–)
Hydrazine and its derivatives
Hydroxides (OH–)
Iron(III) salts
Mercaptans (RHS)
Nitrites (NO2–)
Oxides (CaO, MgO, ZnO, Ag2O, MnO2)
Peroxides (ROOH, ROOR, H2O2)
Selenites (SeO32–)
Silanoles (R3SiOH)
Sulfites (SO32–)
Tellurites (TeO32–)
Thiosulfates (S2O32–)
Tin(II) salts
 Drying oven

Most compounds which undergo side reactions with

iodine can be determined using a drying oven.

Heating the sample evaporates the water. A stream

of dry, inert gas leads the water vapor to the titration
cell, where the amount of water is determined.

D D
C
R S
G
V

G Inert gas (nitrogen, helium, air)

V Control valve
R Gas flowmeter (rotameter) 150 – 200 mL/minute
D Gas drying with silica gel and molecular sieves
S Tubular oven with sample
C Titration cell

Drying oven with gas flowmeter and

gas drying: DO305 and DO337
The drying oven is also suitable for the water
determination of products which are difficult to
dissolve or insoluble and which evolve water
incompletely and only very slowly.

• Plastics
• Mineral oil products
• Inorganic chemicals
• Insoluble organic chemicals
• Foodstuffs (beware of decomposition)
 Troubleshooting

Problem
Titrated solution is dark yellow to brown instead of
bright yellow.
Drift too high after pretitration of the fresh solvent.

Drift too high after titration of a sample. Titration

never ends, long titration time.

Titration never ends, long titration time.

Poor reproducibility of the results.

The results in a series change continuously

(diminishing water content).

Very slow titration with two-component titrant.

Wrong or greatly fluctuating values in the

concentration determination with water.

Increasing value in the concentration determination

with di-sodium tartrate.
Cause. What should be done?
Overtitration. Clean platinum pins of the electrode
with a paper towel.
Titration stand not protected against moisture.
Replace molecular sieves and silica gel in the drying
tube. Check whether titration stand is completely
sealed.
The sample has not dissolved and continuously
evolves water. Use longer stirring time or different
solvent which dissolves the sample or extracts the
water quicker. Side reaction of the sample with
the KF reagent (see section Side reactions).
Use different method (oven, external extraction, etc.).
Wrong termination parameters. Increase value for
drift stop.
Amount of sample too small. Increase amount
of sample to ensure 10 mg water per sample.
(See determination of the amount of sample.)
Water distribution in the sample not
homogeneous: Homogenize sample, if possible
increase amount of sample.
Wrong control parameters. Check control para-
meters and use the optimum control parameters
for the corresponding titrant.
Low water content. With low water contents below
500 ppm, the reproducibility depends primarily on
careful sample preparation and addition. For water
contents below 500 ppm, a KF Coulometer is more
suitable, e.g. DL36 or DL37.
Dissolving capacity of the solvent is exhausted.
Change solvent or use fresh solvent after every
sample.

No more sulfur dioxide in the solvent.

Change solvent.
Water as standard requires practice. The use of
water as a standard for the concentration determi-
nation requires skill and very exact work to obtain
reproducible and accurate results. Determination of
the concentration using di-sodium tartrate or stand-
ard 10.0 is a simpler and more dependable method.
di-sodium tartrate has only limited solubility
(in methanol max. 0.12 g in 40 mL). Replace the
solvent. The concentration determination is correct
only if the di-sodium tartrate has completely
dissolved!